Organic chemistry Books
John Wiley & Sons Inc Stereochemistry of Coordination Compounds
Book SynopsisThis well-illustrated and well-referenced book provides a systematic introduction to the modern aspects of the topographical stereochemistry of coordination compounds, which are made up of metal ions surrounded by other non-metal atoms, ions and molecules.Table of ContentsSurvey of Methods for the Elucidation of the Stereochemistry of Coordination Compounds. Theoretical Bases for the Coordination Geometries of Metal Ions. General Concepts in Topographic Stereochemistry of Coordination Compounds. Topographical Stereochemistry of Mononuclear Coordination Units. Topographical Stereochemistry of Polynuclear Coordination Units. The Stereochemical Course of Reactions of Metal Complexes. Appendices. Index.
£100.76
John Wiley & Sons Inc Practical Organic Mass Spectrometry
Book SynopsisPractical Organic Mass Spectrometry Second Edition A Guide for Chemical and Biochemical Analysis J. R. Chapman Kratos Analytical Instruments, Manchester, UK This volume provides a comprehensive survey of current techniques for the use of mass spectrometry in organic chemical and biochemical analysis. Every aspect of modern instrumentation and technique is discussed. The new edition retains the effective division of material applied in the author''s previous volume-theory, practical requirements and applications. However, it has been thoroughly revised and extended to include all recent advances in mass spectrometry, and is complete with extensive references. This is essentially a book for the practising mass spectroscopist which will appeal to both biochemists and organic chemists. Some familiarity with basic principles is assumed but the author has employed a style which makes this volume suitable for beginners and more advanced students alike. The present volume will be particularly Table of ContentsInstrumentation. Sample Introduction. Chemical Ionization: Ion-Molecule Reactions. Negative Ion Chemical Ionization. The Ionization of Labile Materials I. The Ionization of Labile Materials II. Tandem Mass Spectrometry: The Dissociation of Ions. Quantitative Analysis. Appendices. Index.
£138.56
John Wiley & Sons Inc Theoretical Aspects and Computer Modeling of the
Book SynopsisThe theoretical aspects of crystal packing, the study of the nature and magnitude of the forces that hold molecules together in organic crystals, and of the most favourable arrangements of molecules in crystals are dealt with in this book. After an introductory chapter on the definition and relevance of symmetry in crystal packing, a chapter deals with the physical foundations of weak intermolecular forces and with their simulation by quantum chemical methods. Subsequently, the relationships between crystal structure and crystal thermodynamics are described using empirical intermolecular potentials to bridge the gap by computer modelling.Table of ContentsCrystal Symmetry and Molecular Recognition (A. Gavezzotti). Intermolecular Forces - From the Molecular Charge Distribution to the Molecular Packing (S. Price). Energetic Aspects of Crystal Packing: Experiment and Computer Simulations (A. Gavezzotti & G. Filippini). Energy Minimization and Molecular Dynamics Calculations for Molecular Crystals (B. van Eijck, et al.). Nucleation and Phase Transition in Molecular Clusters: Molecular Dynamics Simulation and Experiment (L. Bartell). Ab Initio Prediction of Possible Molecular Crystal Structures (R. Gdanitz). The Crystal Habit of Molecular Materials: A Structural Perspective (G. Clydesdale, et al.). Index.
£334.76
John Wiley & Sons Inc Emulsion Polymerization and Emulsion Polymers
Book SynopsisEmulsion polymerization is used commercially to produce synthetic alternatives to natural latex rubber. This book provides an up--to--date treatment of all aspects of the field----including basic theory, practice, major industrial uses and related technologies.Table of ContentsPartial table of contents: BASIC SCIENCE. Free-Radical Polymerization (P. Lovell). Features of Emulsion Polymerization (M. El-Aasser & E. Sudol). Stabilization of Polymer Colloid Dispersions (R. Ottewill). THEORY. Harkins, Smith-Ewart and Related Theories (A. Dunn). Modelling Rates, Particle Size Distributions and Molar Mass Distributions (R. Gilbert). PRACTICE. Formulation Components (A. Klein & E. Daniels). Batch and Semi-batch Processes (P. Lovell). Control of Particle Morphology (V. Dimonie, et al.). Process Modelling and Control (F. Schork). Latex Polymer Characterization (A. German, et al.). The Formation and Properties of Latex Films (M. Winnik). MAJOR INDUSTRIAL USES. Diene-based Synthetic Rubbers (D. Blackley). Vinyl Acetate Polymerization (G. Vandezande, et al.). RELATED HETEROGENEOUS POLYMERIZATION. Miniemulsion Polymerization (E. Sudol & M. El-Aasser). Inverse Emulsion and Microemulsion Polymerization (F. Candau). Indexes.
£474.26
John Wiley & Sons Inc Homogeneous Photocatalysis
Book SynopsisPhotocatalysis and related processes occupy a strategic position for the future of Photochemistry. Indeed, applications in solar energy taming, pollution management or other environmental problems and information storage could become practical before the end of this century.Table of ContentsIntroduction to Photocatalysis (M. Chanon M. Schiavello). Fundamentals of Interaction between Light and Matter (J. Mialocq). Homogeneous Proton Transfer Photocatalysis (L. Arnaut S. Formosinho). Principles and Organic Synthetic Applications of Photoinduced Electron Transfer Photosensitization (J. Santamaria C. Ferroud). Transition Metal Complexes and Homogeneous Photocatalytic Transformations of Organic Substrates (C. Kutal). Photocatalytic Aspects of Silver Photography (J. Belloni). Immobilized Photosensitizers and Photocatalysis (M. Julliard). Water Splitting: From Molecular to Supramolecular Photochemical Systems (E. mouyal). Organized Media and Homogeneous Photocatalysis (I. Rico-Lattes A. Lattes). Photosynthesis, a Natural Model for Photocatalysis (P. Mathis).
£353.66
John Wiley & Sons Inc The Chemistry of Free Radicals
Book SynopsisPeroxy radicals are formed in biological systems, the atmosphere and agueous waste and are important intermediates in the breakdown both of organic molecules and several inorganic species. The implications of their chemistry are far reaching and of great importance. Until now their has been no one volume which bring together all aspects of peroxy radical chemistry - from their formation, to their wide and varied chemistry in the aqueous environment, biological systems, solid matrices, polymeric systems and the atmosphere. Peroxy radicals react with CFCs and HFCs in the atmosphere, resulting in the further destruction of the ozone layer - a point which is of topical interest.Table of ContentsPartial table of contents: Formation of Peroxyl Radicals in Solution (Z. Alfassi). Methods of Preparing Organic Peroxy Radicals for Laboratory Studies (O. Nielsen & T. Wallington). The Thermochemistry of Peroxides and Polyoxides, and their Free Radicals (S. Benson & N. Cohen). Ultraviolet Absorption Spectra of Peroxy Radicals in the Gas Phase (O. Nielsen & T. Wallington). Kinetic Studies of Organic Peroxyl Radicals in Aqueous Solutions and Mixed Solvents (Z. Alfassi, et al.). Electron Spin Resonance Studies of Peroxyl Radicals in Solid Matrices (C. Rhodes). Organic Peroxy Radicals in Polymeric Systems (Y. Hori). Peroxy Radicals and the Atmosphere (T. Wallington & O. Nielsen). Peroxyl Radicals in the Treatment of Waste Solutions (N. Getoff). Index.
£600.26
John Wiley & Sons Inc Phosphorus The Carbon Copy
Book SynopsisThis volume discusses the use of phosphorus as a substitute for carbon. The subject is based on the idea that carbon is more similar to its diagonal relative, phosphorus.Table of ContentsThe Phosphorus-Carbon Analogy: Phospha-organic Chemistry. Phosphinidenes (R-P). Terminal Phosphinidene Complexes [R-P=M]. Phosphaalkynes (RCP). Phosphaalkenes, R¯1R¯2C=PR¯3. Phosphapolyenes. Diphosphenes (RP=PR). Phosphorus-Carbon Heterocyclic Chemistry. -Coordination Complexes. What Future for Phosphaorganic Chemistry? Index.
£413.06
John Wiley & Sons Inc Crystallization Processes
Book SynopsisAn overview of crystallization processes of organic and inorganic substances from various homogeneous liquids. Crystal structures, phase transitions and crystallization rates are described in the book in connection with the structure of ions, complexes and molecules of the solution phase.Table of ContentsCrystallization of Electrolytes from the Viewpoint of CoordinationChemistry (K. Waizumi, et al.). Mechanisms of Crystal Growth of Ionic Crystals in Solution:Formation, Transformation, and Growth Inhibition of CalciumCarbonates (K. Sawada). Crystal Growth of Alkali Salts from Concentrated Aqueous Solutions(K. Shigematsu). Molecular Aspects of the Polymorphic Crystallization of Amino Acidsand Lipids (M. Kitamura, et al.). Protein Crystallization at the Initial Stage--Studies onSupersaturated Solutions (M. Ataka). MD Simulations of Crystal Growth from Liquid Metals, AqueousSolutions and Ionic Melts (I. Okada & H. Ohtaki).
£359.96
John Wiley & Sons Inc A Beginners Guide to Mass Spectral Interpretation
Book SynopsisThis book is a logical, step-by-step guide to identification of organic compounds by mass spectrometry. The book is organized into chapters covering the major types of organic compounds, including alcohols, acids and esters, aldehydes and ketones, ethers, hydrocarbons, halogenated compounds, amines and amides, and sulfur-containing compounds. In each chapter, the mechanisms of the major fragmentation pathways are discussed, with reference to several simple sample compounds. By teaching the user to recognize typical fragmentations, the book removes the need to search databases, often limited, of electronic spectra. Key features of the book include: * 200 representative spectra of common organic compounds * Functional group approach to mass spectra interpretation * Appendix of ''unknown'' spectra with step-by-step guide to identification This book is a must for anyone who needs to identify organic molecules by mass spectrometry but does not need to know the detailed workiTrade Review"...an ideal introduction to the topic of spectral interpretation." ----Chromatographia, July 2000Table of ContentsAcknowledgements ix Introduction xi Chapter 1 Isotope Abundances and How We Use Them 1 Chapter 2 Identification of the Molecular Ion 5 Chapter 3 General Interpretation Procedures 9 Chapter 4 Hydrocarbons 22 Chapter 5 Halogenated Hydrocarbons 47 Chapter 6 Alcohols 60 Chapter 7 Ethers and Phenols 72 Chapter 8 Aldehydes and Ketones 79 Chapter 9 Esters and Acids 91 Chapter 10 Nitrogen-Containing Compounds 106 Chapter 11 Thiols and Thioethers 117 Chapter 12 Heterocyclic Compounds 126 Chapter 13 Unknowns 133 Appendix Detailed Solutions to Unknowns 153 Bibliography 180 Topic Index 183 Index of Compounds and Spectra 184
£71.96
Wiley Water Soluble PolyNVinylamides
a huge range and FREE tracked UK delivery on ALL orders.
£341.96
Wiley Oxidizing and Reducing Agents
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£207.86
John Wiley & Sons Inc Organic Syntheses V83
Book SynopsisOrganic Syntheses consists of protocols for the synthesis of useful chemical compounds. Each protocol is repeated in the laboratory of one of the editorial board members for accuracy or for missing experimental details prior to publication.
£75.56
John Wiley & Sons Inc Designing Organic Syntheses A Programmed
Book SynopsisTeaches students to use the language of sythesis directly (utilizing the grammar of synthon and disconnection) rather than translating it into that of organic chemistry.Table of ContentsWhat Do You Need to Know Before You Start? How to Use the Programme. Why Bother with Disconnections? Glossary. Introduction to Disconnections. One-Group Disconnections. Two-Group Disconnections. ``Illogical'' Two-Group Disconnections. General Review Problems. Pericyclic Reactions. Heteroatoms and Heterocyclic Compounds. Special methods for Small Rings: 3- and 4-membered Rings. General Review Problems. Strategy. Further Study. Revision Problems. Problems in Strategy. Problems with Several Published Solutions.
£53.15
John Wiley and Sons Ltd Reaction Mechanisms At a Glance
Book SynopsisStudents at all levels find considerable difficulty in applying their knowledge of organic chemistry to the solution of problems, often relying on memory alone. This book takes a unique approach to show that a general problem-solving strategy is applicable to many of the common reactions. Using a novel ''at-a-glance'' layout, the left-hand page provides a stepwise procedure for working through the reaction mechanisms, with helpful hints about the underlying chemistry, and the facing page contains a fully worked-through answer.Table of ContentsA Note from the author. Introduction. List of Abbreviations. 1. Nucleophilic Substitution and Elimination. 2. Alkene and Alkyne Chemistry. 3. Nucleophilic Additions to Carbonyl Groups. 4. Enolate Chemistry. 5. Aromatic Chemistry. 6. Rearrangements. Index
£34.15
Stanford University Press Experiments Models Paper Tools
Book SynopsisExperimentalization in chemistry was driven by a sign system of chemical formulas invented by the Swedish chemist Jacob Berzelius. By tracing the history of this "paper tool", this work shows how chemistry lost its orientation to natural history.Trade Review"This is a very valuable and stimulating book." -- American Historical Review"[Klein] herself has made a major contribution to the philosophy and the history of chemistry by making clear the existence and the manner of a major but overlooked transformation in organic chemistry. Methodologically and substantively, this is a significant achievement." -- Canadian Journal of History"Experiments, Models, Paper Tools is a clear and compelling account of an important epoch in the history of organic chemistry, as well as a fine demonstration and elaboration of Klein's most fruitful investigation into the special role of systems of representation in the history of chemistry." -- Annals of Science"...an original contribution to the history of chemistry and a fascinating book....clearly presented, intellectually stimulating, and a pleasure to read." -- British Journal of the History of ScienceTable of ContentsPreface Introduction 1. The Semiotics of Berzelian Chemical Formulas The Various Meanings of Berzelian Formulas Image and Language: The Syntax of Berzelian Formulas 2. Two Cultures of Organic Chemistry in the Nineteenth Century: A Structural Comparison The Area of Research Objects in Early Nineteenth-Century Plant and Animal Chemistry Plant and Animal Substances: A Cross between Natural History and Chemistry The Classification of Plant and Animal Substances "Nature" and "Art" in the Experimental Practice of Plant and Animal Chemistry The Experimental Culture of Organic Chemistry after 1840 The Two Forms of Organic Chemistry Compared 3. Experiments on the Periphery of Plant Chemistry Ether Production and Commercial Pharmacy Interpretive Models of the Formation of Ordinary Ether around 1800 Quantitative Approaches in the Study of Organic Reactions Simplified Quantitative Experiments The Manufacture of an Artificial Oil in the Chemical Laboratory New Attempts to Balance the Masses of Reacting Substances The Overthrow of the Accepted Interpretive Model of the Formation of Ordinary Ether 4. Paper Tools for the Construction of Interpretive Models of Chemical Reactions The Historical Problem Modeling Separate Reaction Pathways The Performative Function of Berzelian Formulas 5. Paper Tools for the Classification of Organic Substances The Structure and Function of Dumas and Boullay's Table Experimentation and the Construction of Formula Models for the "Compounds of Bicarbonated Hydrogen" The Enlargement of Substance Classes by the Construction of Further Formula Models Manipulations of Formulas and Their Significance Reception of the New Classification among European Chemists 6. Paper Tools for Modeling the Constitution of Organic Compounds The Shared Conceptual Preconditions for the Models of Constitution Models of Constitution Prior to 1833 The Controversy 7. The Dialectic of Tools and Goals A Performative Account of Conceptual Development The Creation of Mutual Adjustments and Its Reflection in the New Mode of Justification 8. The Historical Transformation Process Model Objects and Unintended Paradigmatic Achievements The Structural Transformation 9. Paper Tools Filling in the Gaps of Inscription Devices Chains of Inscriptions and Paper Tools Notes Literature Cited Index
£62.90
John Wiley & Sons Inc Stereoselective Synthesis of Drugs and Natural
Book SynopsisBrings together the best tested and proven stereoselective synthetic methods Both the chemical and pharmaceutical industries are increasingly dependent on stereoselective synthetic methods and strategies for the generation of new chiral drugs and natural products that offer specific 3-D structures. With the publication of Stereoselective Synthesis of Drugs and Natural Products, researchers can turn to this comprehensive two-volume work to guide them through all the core methods for the synthesis of chiral drugs and natural products. Stereoselective Synthesis of Drugs and Natural Products features contributions from an international team of synthetic chemists and pharmaceutical and natural product researchers. These authors have reviewed the tremendous body of literature in the field in order to compile a set of reliable, tested, and proven methods alongside step-by-step guidance. This practical resource not only explores synthetic methodology, but Trade Review“The work will also be very useful to those actively involved in the teaching of modern organic chemistry and synthetic methodologies, because it allows one to quickly compile several examples of applications of methods for a lecture and include details of the corresponding transition states without the need to obtain the original publications.” (Angew. Chem. Int. Ed, 1 May 2014) Table of ContentsPreface List of contributors List of symbols and abbreviations PART 1: GENERAL METHODS AND STRATEGIES Chapter 1: Principles, concepts and strategies of stereoselective synthesis Vasyl Andrushko and Natalia Andrushko Chapter 2: Chiral auxiliaries in drug synthesis Stanley Chang, Shira D. Halperin, Jarod Moore and Robert Britton Chapter 3: Solid-phase organic synthesis of drugs and natural products Peter J. H. Scott Chapter 4: Asymmetric phase-transfer catalysis Kohsuke Ohmatsu, Daisuke Uraguchi, and Takashi Ooi Chapter 5: Microwave-assisted stereoselective synthesis Yoann Coquerel, Evelina Colacino, Jean Rodriguez, Jean Martinez and Frédéric Lamaty Chapter 6: Application of micro reactor methodology for organic synthesis Paul Watts and Charlotte Wiles PART 2: STEREOSELECTIVE SYNTHESIS BY BOND FORMATION 2.1. STEREOSELECTIVE METHODS FOR C–C BOND FORMATION Chapter 7: Asymmetric α-alkylation of aldehydes, ketones and carboxylic acids Mark C. Kohler, Sarah E. Wengryniuk, and Don M. Coltart Chapter 8: Asymmetric aldol reactions in the total syntheses of natural products Seijiro Hosokawa Chapter 9: Asymmetric Michael addition and related reactions Pengfei Li, Jun Wang and Fuk Yee Kwong Chapter 10: Construction of polypropionate fragments in natural product synthesis Maris Turks, Sylvain Laclef and Pierre Vogel Chapter 11: Organocatalytic conjugate addition in stereoselective synthesis Adrien Quintard and Alexandre Alexakis Chapter 12: Stereoselective Nozaki-Hiyama-Kishi reaction Pat Guiry and Gráinne Hargaden Chapter 13: Transition-metal-catalyzed asymmetric C–C cross-couplings in stereoselective synthesis Vasiliki Sarli Chapter 14: Asymmetric hydroformylation, hydroxy- and alkoxycarbonylation for stereoselective synthesis Jamie T. Durrani and Matthew L. Clarke Chapter 15: Intramolecular oxycarbonylation in stereoselective synthesis Tibor Gracza Chapter 16: Stereoselective cycloaddition reactions Tae-Kyung Lee and Jung-Mo Ahn Chapter 17: Sigmatropic rearrangements in stereoselective synthesis Brinton Seashore-Ludlow and Peter Somfai Chapter 18: Ring contraction reactions in the total synthesis of biologically active natural products Luiz F. Silva Jr. Chapter 19: Electrocyclic reactions in stereoselective synthesis Marcus A. Tius Chapter 20: Transannular cyclization in natural product total synthesis Jiong Yang and Haoran Xue Chapter 21: Cascade reactions in stereoselective synthesis Bor-Cherng Hong and Nitin S. Dange Chapter 22: Sulfur dioxide: a powerful tool for the stereoselective construction of C-C bonds Pierre Vogel, Dean Markovic and Mâris Turks Chapter 23: Transition metal C-H activation: application to stereoselective synthesis of natural products and drugs Mickaël Jean and Pierre van de Weghe Chapter 24: Metathesis reactions in drug and natural product synthesis Akio Saito, Yuji Hanzawa Chapter 25: Radicals in stereoselective C-C bond formation Josep Bonjoch, Ben Bradshaw and Faïza Diaba Chapter 26: Trifluoromethyl (CF3) group insertion methods in stereoselective synthesis Tsutomu Konno Chapter 27: Stereoselective organocatalyzed C–C bond-forming reactions Kazuo Nagasawa and Koji Yasui Chapter 28: Enzyme-catalysed stereoselective C–C bond formation reactions in total syntheses Adeline Ranoux and Ulf Hanefeld 2.2. STEREOSELECTIVE METHODS FOR C–H BOND FORMATION Chapter 29: Stereoselective hydrogenation of C=C bonds: application to drug and natural product synthesis Natalia Andrushko and Vasyl Andrushko Chapter 30: Asymmetric hydrogenation of C=O and C=N bonds in stereoselective synthesis Natalia Andrushko and Vasyl Andrushko Chapter 31: Asymmetric protonation of carbanions and polar double bonds: application to total syntheses Thomas Poisson and Shu Kobayashi Chapter 32: Organocatalytic reduction in stereoselective synthesis Felix Kortmann and Adriaan Minnaard Chapter 33: Biocatalytic asymmetric reduction of C=O and activated C=C bonds in stereoselective synthesis Tomoko Matsuda, Rio Yamanaka and Kaoru Nakamura 2.3. STEREOSELECTIVE METHODS FOR C–O BOND FORMATION Chapter 34: Transition-metal-catalyzed stereoselective oxidations in drug and natural product synthesis Alessandro Scarso and Giorgio Strukul Chapter 35: Asymmetric epoxidation in stereoselective synthesis Zhicai Yang Chapter 36: Biocatalytic asymmetric oxidations in stereoselective synthesis Anett Schallmey, Pablo Dominguez de Maria and Paula Bracco Chapter 37: Ether transfer methodology: application to the synthesis of polyketide natural products Eric Stefan and Richard E. Taylor Chapter 38: Stereoselective formation of 2-deoxyglycosidic bonds in biologically active natural products Daisuke Takahashi and Kazunobu Toshima 2.4. STEREOSELECTIVE METHODS FOR C–N BOND FORMATION Chapter 39: Asymmetric hydroamination and reductive amination in total synthesis Manas K. Ghorai, Deo Prakash Tiwari and Aditya Bhattacharyya Chapter 40: Carboamination and alkylative cyclization with C-N bond formation in stereoselective syntheses Manas K. Ghorai, Sandipan Halder and Sauvik Samanta Chapter 41: Cycloadditions with stereoselective C-N bond formation in total syntheses Guillaume Vincent 2.5. STEREOSELECTIVE FORMATION OF OTHER C–HETEROATOM AND OTHER BONDS Chapter 42: Stereoselective halogenations Chong Kiat Tan, Yi Zhao, Jing Zhou and Ying-Yeung Yeung Chapter 43: Stereoselective synthesis of halogenated natural products Takehiko Yoshimitsu Chapter 44: Asymmetric fluorination methods: application in the stereoselective synthesis of fluorinated drugs Vincent Bizet and Dominique Cahard Chapter 45: Enzymatic halogenation in stereoselective synthesis Cormac D. Murphy and Benjamin R. Clark Chapter 46: Stereoselective carbon–sulfur (C–S) bond formation Kyungsoo Oh Chapter 47: Stereoselective methods for carbon-phosphorus (C–P) bond formation Marcin Kalek and Jacek Stawinski Chapter 48: Transition-metal-catalyzed asymmetric sulfoxidation in drug and natural product synthesis Alessandro Scarso and Giorgio Strukul PART 3: METHODS OF ANALYSIS AND CHIRAL SEPARATION Chapter 49: NMR-Spectroscopy in drug and natural product analysis Stanisuaw Witkowski and Iwona Wawer Chapter 50: Determination of enantiomeric purity and absolute configuration by NMR spectroscopy Thomas J. Wenzel Chapter 51: Solid-state NMR spectroscopy in drug design and discovery David A. Middleton and Simon G. Patching Chapter 52: Capillary electrophoresis in chiral separations Ans Hendrickx, Debby Mangelings and Yvan Vander Heyden Chapter 53: Determination of absolute configuration using chiroptical methods Joao Marcos Batista, Jr. Chapter 54: Chiral chromatographic methods in the analysis and purification of enantiomers Arnau Novell and Cristina Minguillón Chapter 55: X-Ray crystallography and 1H NMR anisotropy methods for determination of absolute configurations Nobuyuki Harada Chapter 56: Crystallization based separation of enantiomers Yaling Wang and Alex Chen Chapter 57: Enzymatic dynamic kinetic resolution in stereoselective synthesis Francisca Rebolledo, Javier González-Sabín, and Vicente Gotor Subject index
£409.46
John Wiley & Sons Inc Organic Syntheses Volume 88
Book SynopsisThe current volume continues the tradition of the Organic Synthesis series, providing carefully checked and edited experimental procedures that describe important synthetic methods, transformations, reagents, and synthetic building blocks or intermediates with demonstrated utility in organic synthesis. These significant and interesting procedures should prove worthwhile to many synthetic chemists working in increasingly diverse areas. A trusted guide for professionals in organic and medicinal chemistry in academia, government, and industries, including phar-maceuticals, fine chemicals, agrochemicals, and biotech.Table of ContentsEditorial: Organic Syntheses: The “Gold Standard” for Experimental Synthetic Organic Chemistry 1 Rick L. Danheiser α-Arylation of Esters Catalyzed by the Pd(I) Dimer [P(t-Bu)3Pd(µ-Br)] 4 David S. Huang, Ryan J. DeLuca, and John F. Hartwig The Preparation of Amides by Copper-medicated Oxidative Coupling of Aldehydes and Amine Hydrochloride Salts 14 Maxime Giguère-Bisson, Woo-Jin Yoo, and Chao-Jun Li Synthesis of 2-Aryl Pyridines by Palladium-Catalyzed Direct Arylation of Pyridine N-Oxides 22 Louis-Charles Campeau and Keith Fagnou The Preparation of Indazoles via Metal Free Intramolecular Electrophilic Animation of 2-Aminophenyl Ketoximes 33 Carla M. Councellar, Chad C. Eichman, Brenda C. Wray, Eric R. Welin, and James P. Stambuli The Preparation of (2R,5S)-2-t-Butyl-3,5-Dimethylimidazolidin-4-One 42 Thomas H. Graham, Benjamin D. Horning, and David W. C. MacMillan Synthesis of Et2SB•SbCl5Br and Its Use in Biomimetic Brominative Polyene Cyclizations 54 Scott A. Snyder and Daniel S. Treitler Discussion Addendum for: Asymmetric Synthesis of (M)-2- Hydroxymethyl-1-(2-Hydroxy-3,6-Dimethylphenyl)Naphthalene via a Configurationally Unstable Biaryl Lactone 70 G. Bringmann, T. A. M. Gulder, and T. Gulder Synthesis of Lithium 2-Pyridyltriolborate and Its Cross-Coupling Reaction with Aryl Halides 79 Yasunori Yamamoto, Juugaku Sigai, Miho Takizawa, and Norio Miyaura Synthesis of (+)-B-Allyldiisopinocampheylborane and It Reaction with Aldehydes 87 Huikai Sun and William R. Roush Discussion Addendum for: Palladium-Catalyzed Cross-Coupling of (Z)-1-Heptenyldimethylsilanol with 4-Iodoanisole: (Z)-(1-Heptenyl)-4-Methoxybenzene 102 Scott E. Denmark and Jack Hung-Chang Liu The Preparation of Cyclohept-4-Enones by Rhodium-Catalyzed Intermolecular [5+2] Cycloaddition 109 Paul A. Wender, Adam B. Lesser, and Lauren E. Sirois Organocatalytic Enantioselective Synthesis of Bicyclic ß-Lactones from Aldehyde Acids via Nucleophile-Catalyzed Aldol-Lactonization (NCAL) 121 Henry Nguyen, Seongho Oh, Huda Henry-Riyad, Diana Sepulveda, and Daniel Romo Phosphine-Catalyzed [3 + 2) Annulation: Synthesis of Ethyl 5-(tert-Butyl)-2-Phenyl-1-Tosyl-3-Pyrroline-3-Carboxylate 138 Ian P. Andrews and Ohyun Kwon Preparation of Horner-Wadsworth-Emmons Reagent: Methyl 2-Benzyloxycarbonylamino-2-(Dimethoxy-Phosphinyl)Acetate 152 Hiroki Azuma, Kentaro Okano, Tohru Fukuyama, and Hidetoshi Tokuyama Discussion Addendum for: 5-ENDO-TRIG Cyclization of 1,1-Difluoro-1-Alkenes: Synthesis of 3-Butyl-2-Fluoro-1-Tosylindole (1H-Indole, 3-Butyl-2-Fluoro-1-[(4-Methylphenyl)Sulfonyl-) 162 Junji Ichikawa Preparation of a Thrifluoromethyl Transfer Agent: 1-Trifloromethyl-1,3-Dihydro-3,3-Dimenthyl-1,2-Benziodoxole 168 Patrick Eisenberger, Iris Kieltsch, Raffael Koller, Kyrill Stanek, and Antonio Tongni Synthesis of (S,S)-Diisopropyl Tartrate (E)-Crothylboronate and Its Reaction with Aldehydes: (2R,3R,4R)-1,2-Dideoxy-2-Ethenyl-4,5,-O-(1-Methylethylidene)-Xylitol 181 Huikai Sun and William R. Roush Discussion Addendum for: 4-Methoxy-4’-Nitrophenyl. Recent Advances in the Stille Biaryl Coupling Reaction and Applications in Complex Natural Products Synthesis 197 Robert M. Williams Discussion Addendum for: Palladium-Catalyzed Reaction of 1-Alkenylboronates with Vinylic Halides: (1Z,3E)-1-Phenyl-1,3-Octadiene 202 Norio Miyaura Discussion Addendum for: Palladium (0)-Catalyzed Reaction of 9-Alkyl-9-Borabicyclo[3.3.1]Nonane with 1-Bromo-1-Phenylthioethene: 4-(3-Cyclohexenyl )-2-Phenylthio-1-1-Butene 207 Norio Miyaura Preparation of Isopropyl 2-Diazoacetyl(Phenyl)Carbamate 212 Hubert Muchalski, Amanda B. Doody, Timothy L. Troyer, and Jeffrey N. Johnson Gram Scale Catalytic Asymmetric Aziridination: Preparation of (2R,3R)-Ethyl 1-Benzhydryl-3-(4-Bromopheneyl)Aziridine 2-Carboxylate 224 Aman A. Desai, Roberto Morán-Ramallal, and William D. Wulff Cu-Catalyzed Azide-Alkyne Cycloaddition: Preparation of Tris((1-Benzyl-1H-1,2,3-Triazolyl )Methyl)Amine 238 Jason E. Hein, Larissa B. Krasnova, Masayuki Iwasaki, and Valery V. Fokin Lithiated Primary Alkyl Carbamates for the Homologation of Boronic Esters Matthew P. Webster, Benjamin M. Partridge, and Varinder K. Aggarwal Discussion Addendum for: Palladium-Catalyzed Reduction of Vinyl Trifluoromethanesulfonates to Alkenes: Cholesta-3,5-Diene 260 Sandro Cacchi, Enrico Morera, and Giorgio Ortar Discussion Addendum for: Synthesis of Indoles by Palladium-Catalyzed Reductive N-Heteroannulation of 2-Nitrostyrenes: Methyl Indole-4-Carboxylate 291 Björn C. Söderberg An Economical Synthesis of 4-Trimethysilyl-2-Butyn-1-OL 296 Alexander N. Wein, Rongbiao Tong, and Frank E. McDonald Silver-Catalyzed Rearrangement of Propargylic Sulfinates: Synthesis of Allengic Sulfones 309 Michael Harmata, Zhengxin Cai and Chaofeng Huang (Sa,S)-N-[2’-(Methylphenylsulfonamido)-1-1’-Binaphthyl-2-YL]Pyrrolidine-2-Carboxamide: An Organocatalyst for the Direct Aldol Reaction 317 Santiago F. Viózquez, Gabriela Guillene, Carmen Nájera, Ben Bradshaw, Gorka Etxebarria-Jardi, and Josep Bonjoch Synthesis of (S)-8a-Methyl-3,4,8,8a-Tetrahydro-1,6-(2H,7H)-Naphthalenedione via N-Tosyl-(Sa)-Binam-L-Pholinamide Organocatalysis 330 Ben Bradshaw, Gorka Etxebarria-Jardi, Josep Bonjoch, Santiago F. Viózquez, Gabriela Guillena, and Carmen Nájera Stereoselective Nickel-Catalyzed 1,4-Hydroboration of 1,3-Dienes 342 Robert J. Ely and James P. Morken Tandem Nucleophilic Addition/Fragmentation of Vinylogous Acyl Triflates: 2-Methyl-2-(1-Oxo-5-Heptynyl)-1-3-Dithiane 353 Marilda P. Lisboa, Tunf T. Hoang, and Gregory B. Dudley Synthesis and Diasteroselective Aldol Reactions of a Thiazolidinethione Chiral Auxiliary 364 Michael T. Crimmins, Hamish S. Christie, and Colin O. Hughes Synthesis of 2,3-Disubstituted Indoles via Palladium-Catalyzed Annulation of Internal Alkynes: 3-Methyl-2-(Trimethylsilyl)Indole 377 Yu Chen, Nataliya A. Markina, Tuanli Yao, and Richard C. Larock An Intramolecular Amination of Aryyl Halides with a Combination of Copper (I) and Cesium Acetate: Preparation of 5,6-Dimethoxyindole-1,2-Dicarboxylic Acid 1-Benzyl Ester 2-Methyl Ester 388 Toshiharu Noji, Kentaro Okano, Tohru Fukuyama, and Hidetoshi Tokuyama Ligand-Free Copper(II) Oxide Nanoparticles-Catalyzed Synthesis of Substituted Benzoxazoles 398 Prasenjit Saha, Md Ashif Ali, and Tharmalingam Punniyamurthy (R)-3,3’-Bis(9-Phenanthyryl)-1,1’-Binaphthalene-2,2’-Diyl Hydrogen Phosphate 406 Wenhao Hu, Jing Zhou, Xinfang Xu, Weijun Liu, and Liuzhu Gong Enantioselective Three-Component Reaction for the Preparation of ß-Amino-a-Hydroxy Esters 418 Jing Zhou, Xinfang Xu, and Wenhao Hu Mild Conversion of Tertiary Amides to Aldehydes Using Cp2Zr(H)Cl (Schwartz’s Reagent) 427 Matthew W. Leighty, Jared T. Spletstoser, and Gunda I. Georg
£63.86
John Wiley & Sons Inc Organic Reactions Volume 78
Book SynopsisThis volume in the venerable Organic Reactions series contains three chapters focusing on the introduction or the removal of nitrogen from organic compounds. The first chapter features a classic chemical reaction for introducing nitrogen into organic compounds, namely the Schmidt Reaction. The second chapter highlights a less-well-known yet fascinating transformation that introduces nitrogen into organic compounds, The Neber Rearrangement. The third chapter describes an unusual class of reactions that involve the loss of small molecular fragments from a ring, where separate carbon atoms unite to form alkenes.Table of ContentsCHAPTER PAGE 1. THE SCHMIDT REACTION Aaron Wrobleski, Thomas C. Coombs, Chan Woo Huh, Sze-Wan Li, and Jeffrey Aub´e 1 2. THE NEBER REARRANGEMENT William F. Berkowitz 321 3. TWOFOLD EXTRUSION REACTIONS Lynn James Guziec and Frank S. Guziec, Jr 411 CUMULATIVE CHAPTER TITLES BY VOLUME 551 AUTHOR INDEX, VOLUMES 1–78 567 CHAPTER AND TOPIC INDEX, VOLUMES 1–78 573
£117.00
John Wiley & Sons Inc How To Solve Organic Reaction Mechanisms
Book SynopsisHow To Solve Organic Reaction Mechanisms: A Stepwise Approach is an upgraded and much-expanded sequel to the bestselling text Reaction Mechanisms at a Glance.Table of ContentsPreface vi Abbreviations vii About the companion website viii Introduction ix 1 Nucleophilic substitution and elimination 1 2 Alkene and alkyne chemistry 32 3 Nucleophilic additions to carbonyl groups 64 4 Enolate chemistry 96 5 Aromatic chemistry 128 6 Rearrangements 160 7 Ligand coupling processes 192 Index 224
£35.10
John Wiley & Sons Inc Organic Reactions Volume 79
Book SynopsisVolume 79 in the venerable Organic Reactions series contains two chapters. The first addresses cross-coupling reactions of organotrifluoroborate salts, useful in the development of natural products, materials, and pharmacologically active substances.Table of Contents1. CROSS-COUPLING REACTIONS OF ORGANOTRIFLUOROBORATE SALTS Gary A. Molander and Ludivine Jean-Gerard 1 2. ASYMMETRIC TRANSFORMATIONS BY DEPROTONATION USING CHIRAL LITHIUM AMIDES Nigel S. Simpkins and Michael D. Weller 317 CUMULATIVE CHAPTER TITLES BY VOLUME 637 AUTHOR INDEX, VOLUMES 1–79 653 CHAPTER AND TOPIC INDEX, VOLUMES 1–79 659
£137.70
John Wiley & Sons Inc Organic Reactions Volume 81
Book SynopsisVolume 81 represents the confluence of two rare and important phenomena for chapters in the Organic Reactions series, namely, it is a single-chapter volume, and it contains a name reaction coauthored by the inventor. Of the 261 chapters published thus far, only seven have been of sufficient impact to appear as single-chapter volumes. The single chapter in this volume entitled The Krapcho Dealkoxycarbonylation Reaction of Esters with a-Electron-Withdrawing Substituents has been coauthored by A. Paul Krapcho together with Organic Reactions'' long-time contributor Engelbert Ciganek. The Krapcho Decarboxylation, as it is known in common parlance, is an extraordinarily useful alternative to the classical hydrolysis-decarboxylation of esters bearing a-electron-withdrawing substituents. This process replaces the strongly basic or acidic conditions normally required for ester saponification with the neutral cleavage of the ester group by a BAC2 mechaniTable of Contents1 THE KRAPCHO DEALKOXYCARBONYLATION REACTION OF ESTERS WITH α-ELECTRON-WITHDRAWING SUBSTITUENTS A Paul Krapcho and Engelbert Ciganek 1 CUMULATIVE CHAPTER TITLES BY VOLUME 537 AUTHOR INDEX, VOLUMES 1–81 553 CHAPTER AND TOPIC INDEX, VOLUMES 1–81 559
£133.20
John Wiley & Sons Inc Organic Reactions Volume 82
Book SynopsisVolume 82 describe reactions that involve one of the most common transformations in organic chemistry, namely, the pairwise combination of double bonded functional groups. The importance of this enormous family of reactions is a reflection of the spectacular diversity of precursors and products that can arise from appropriate modulation of reactivity of the partners and especially selection of reagents that dictate the outcome. The first chapter authored by Takeshi Takeda and Akira Tsubouchi describes the combination of carbonyl compounds in the presence of highly reactive, low valent titanium reagents in the classic McMurry reaction. The second chapter concerns the chemistry of highly-reactive, double-bonded functional groups, namely ketenes.Table of Contents1. THE McMURRY COUPLING AND RELATED REACTIONS Takeshi Takeda and Akira Tsubouchi 1 2. CATALYTIC ASYMMETRIC KETENE [2+ 2] AND [4+ 2] CYCLOADDITIONS Scott G. Nelson, Robert D. Dura, and Timothy J. Peelen 471 CUMULATIVE CHAPTER TITLES BY VOLUME 623 AUTHOR INDEX, VOLUMES 1–82 639 CHAPTER AND TOPIC INDEX, VOLUMES 1–82 645
£133.20
John Wiley & Sons Inc Organic Reaction Mechanisms 2013
Book Synopsis* The 49th annual volume in this highly successful series * Surveys the development in understanding of the main classes of organic reaction mechanisms reported in the primary scientific literature in 2013 * Mechanisms of stereo-specific reactions are highlighted.Table of Contents1. Reactions of Aldehydes and Ketones and Their Derivatives by B. A. Murray 1 2. Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and Their Derivatives by C. T. Bedford 67 3. Oxidation and Reduction by R. N. Mehrotra 91 4. Carbenes and Nitrenes by E. Gras and S. Chassaing 177 5. Aromatic Substitution by M. R. Crampton 217 6. Carbocations by D. A. Klumpp 273 7. Nucleophilic Aliphatic Substitution by K. C. Westaway 321 8. Carbanions and Electrophilic Aliphatic Substitution by M. L. Birsa 361 9. Elimination Reactions by M. L. Birsa 383 10. Addition Reactions: Polar Addition by P. Ko¡covsk´y 393 11. Addition Reactions: Cycloaddition by N. Dennis 483 12. Molecular Rearrangements by J. M. Coxon 519 Author Index 609 Subject Index 651
£371.66
John Wiley & Sons Inc Organic Syntheses Volume 89
Book SynopsisThe current volume continues the tradition of providing significant and interesting procedures, which should prove worthwhile to many synthetic chemists working in increasingly diverse areas. Following precedent, there is no specific or central theme to this volume.
£83.66
John Wiley & Sons Inc Guide To Fluorine Nmr For Organic Chemists Second
Book SynopsisFollowing its well-received predecessor, this book offers an essential guide to chemists for understanding fluorine in spectroscopy. With over 1000 compounds and 100 spectra, the second edition adds new data featuring fluorine effects on nitrogen NMR, chemical shifts, and coupling constants.Table of ContentsPREFACE xv 1 GENERAL INTRODUCTION 1 1.1. Why Fluorinated Compounds are Interesting? / 1 1.1.1. Steric Size / 1 1.1.2. Polar Effects / 2 1.1.3. Effect of Fluorine Substituents on Acidity and Basicity of Compounds / 2 1.1.4. Effect of Fluorinated Substituents on Lipophilicity of Molecules / 3 1.1.5. Other Effects / 4 1.1.6. Analytical Applications in Biomedicinal Chemistry / 4 1.2. Introduction to Fluorine NMR / 5 1.2.1. Chemical Shifts / 5 1.2.2. Coupling Constants / 7 2 AN OVERVIEW OF FLUORINE NMR 9 2.1. Introduction / 9 2.2. Fluorine Chemical Shifts / 10 2.2.1. Some Aspects of Shielding/Deshielding Effects on Fluorine Chemical Shifts / 11 2.2.2. Solvent Effects on Fluorine Chemical Shifts / 15 2.2.3. Overall Summary of Fluorine Chemical Shift Ranges / 16 2.3. The Effect of Fluorine Substituents on Proton Chemical Shifts / 17 2.4. The Effect of Fluorine Substituents on Carbon Chemical Shifts / 18 2.5. The Effect of Fluorine Substituents on 31P Chemical Shifts / 19 2.6. The Effect of Fluorine Substituents on 15N Chemical Shifts / 20 2.7. Spin–Spin Coupling Constants to Fluorine / 23 2.7.1. Effect of Molecule Chirality on Coupling / 27 2.7.2. Through-Space Coupling / 29 2.7.3. Fluorine–Fluorine Coupling / 32 2.7.4. Coupling Between Fluorine and Hydrogen / 33 2.7.5. Coupling Between Fluorine and Carbon / 35 2.7.6. Coupling Between Fluorine and Phosphorous / 38 2.7.7. Coupling Between Fluorine and Nitrogen / 39 2.8. Second-Order Spectra / 40 2.9. Isotope Effects on Chemical Shifts / 45 2.10. Advanced Topics / 48 2.10.1. Multidimensional 19F NMR / 50 3 THE SINGLE FLUORINE SUBSTITUENT 55 3.1. Introduction / 55 3.1.1. Chemical Shifts – General Considerations / 56 3.1.2. Spin–Spin Coupling Constants – General Considerations / 56 3.2. Saturated Hydrocarbons / 57 3.2.1. Primary Alkyl Fluorides / 57 3.2.2. Secondary Alkyl Fluorides / 61 3.2.3. Tertiary Alkyl Fluorides / 63 3.2.4. Cyclic and Bicyclic Alkyl Fluorides / 66 3.3. Influence of Substituents/Functional Groups / 70 3.3.1. Halogen Substitution / 70 3.3.2. Alcohol, Ether, Epoxide, Ester, Sulfide, Sulfone, Sulfonate, and Sulfonic Acid Groups / 77 3.3.3. Amino, Ammonium, Azide, and Nitro Groups / 80 3.3.4. Phosphorous Compounds / 83 3.3.5. Silanes, Stannanes, and Germanes / 83 3.4. Carbonyl Functional Groups / 84 3.4.1. Aldehydes and Ketones / 85 3.4.2. Carboxylic Acid Derivatives / 86 3.4.3. 1H and 13C NMR Data for Aldehydes, Ketones, and Esters / 86 3.4.4. β-Ketoesters, Diesters, and Nitroesters / 89 3.5. Nitriles / 89 3.5.1. 1H and 13C NMR Data for Nitriles / 89 3.6. Alkenes with a Single Fluorine Substituent / 90 3.6.1. Hydrocarbon Alkenes / 90 3.6.2. Conjugated Alkenyl Systems / 93 3.6.3. Allylic Alcohols, Ethers, and Halides / 94 3.6.4. Halofluoroalkenes and Fluorovinyl Ethers / 97 3.6.5. Geminal Fluoro, Hetero Alkenes / 98 3.6.6. Multifluoroalkenes / 98 3.6.7. α,β-Unsaturated Carbonyl Compounds / 101 3.7. Acetylenic Fluorine / 104 3.8. Allylic and Propargylic Fluorides / 105 3.8.1. 1H and 13C NMR Data / 106 3.9. Fluoroaromatics / 106 3.9.1. Monofluoroaromatics / 106 3.9.2. Fluoropolycyclic Aromatics: Fluoronaphthalenes / 111 3.9.3. Polyfluoroaromatics / 112 3.10. Fluoromethyl Aromatics / 114 3.11. Fluoroheterocycles / 119 3.11.1. Fluoropyridines, Quinolines, and Isoquinolines / 119 3.11.2. Fluoropyrimidines and Other Fluorine-Substituted Six-Membered Ring Heterocycles / 122 3.11.3. Fluoromethyl Pyridines and Quinolines / 123 3.11.4. Fluoropyrroles and Indoles / 123 3.11.5. Fluoromethyl Pyrroles and Indoles / 125 3.11.6. Fluorofurans and Benzofurans / 125 3.11.7. Fluoromethyl Furans and Benzofurans / 126 3.11.8. Fluorothiophene and Benzothiophene / 127 3.11.9. Fluoromethyl Thiophenes and Benzothiophenes / 128 3.11.10. Fluoroimidazoles and Pyrazoles / 128 3.11.11. Fluoromethyl and Fluoroalkyl Imidazoles, 1H-pyrazoles, Benzimidazoles, 1H-triazoles, Benzotriazoles, and Sydnones / 128 3.12. Other Common Groups with a Single Fluorine Substituent / 129 3.12.1. Acyl Fluorides / 130 3.12.2. Fluoroformates / 131 3.12.3. Sulfinyl and Sulfonyl Fluorides / 131 4 THE CF2 GROUP 133 4.1. Introduction / 133 4.1.1. Chemical Shifts – General Considerations / 134 4.1.2. Spin–Spin coupling Constants – General Considerations / 135 4.2. Saturated Hydrocarbons Containing a CF2 Group / 135 4.2.1. Alkanes Bearing a Primary CF2H Group / 136 4.2.2. Secondary CF2 Groups / 139 4.2.3. Discussion of Coupling Constants Within CF2 Groups / 142 4.2.4. Pertinent 1H Chemical Shift Data / 143 4.2.5. Pertinent 13C NMR Data / 146 4.3. Influence of Substituents/Functional Groups / 148 4.3.1. Halogen Substitution / 148 4.3.2. Alcohol, Ether, Esters, Thioether, and Related Substituents / 152 4.3.3. Epoxides / 155 4.3.4. Sulfoxides, Sulfones, Sulfoximines, and Sulfonic Acids / 156 4.3.5. Multifunctional β,β-Difluoro Alcohols / 157 4.3.6. Compounds with Two Different Heteroatom Groups Attached to CF2 Including Chloro- and Bromodifluoromethyl Ethers / 157 4.3.7. Amines, Azides, and Nitro Compounds / 158 4.3.8. Phosphines, Phosphonates, and Phosphonium Compounds / 162 4.3.9. Silanes, Stannanes, and Germanes / 162 4.3.10. Organometallics / 162 4.4. Carbonyl Functional Groups / 164 4.4.1. Aldehydes and Ketones / 164 4.4.2. Carboxylic Acids and Derivatives / 166 4.5. Nitriles / 168 4.5.1. 1H and 13C NMR Spectra of Nitriles / 168 4.6. Amino-, Hydroxyl-, and Keto-Difluorocarboxylic Acid Derivatives / 169 4.7. Sulfonic Acid Derivatives / 170 4.8. Alkenes and Alkynes / 170 4.8.1. Simple Alkenes with Terminal Vinylic CF2 Groups / 170 4.8.2. Conjugated Alkenes with Terminal Vinylic CF2 Group / 172 4.8.3. Cumulated Alkenes with a Terminal CF2 Group / 174 4.8.4. Effect of Vicinal Halogen or Ether Function / 174 4.8.5. Effect of Allylic Substituents / 174 4.8.6. Polyfluoroethylenes / 175 4.8.7. Trifluorovinyl Group / 175 4.8.8. α,β-Unsaturated Carbonyl Systems with a Terminal Vinylic CF2 Group / 176 4.8.9. Allylic and Propargylic CF2 Groups / 177 4.9. Benzenoid Aromatics Bearing a CF2H or CF2R Group / 178 4.9.1. 1H and 13C NMR Data / 179 4.9.2. CF2 Groups with More Distant Aryl Substitutents / 180 4.10. Heteroaromatic CF2 Groups / 180 4.10.1. Pyridines, Quinolones, Phenanthridines, and Acridines / 181 4.10.2. Furans, Benzofurans, Thiophenes, Pyrroles, and Indoles / 181 4.10.3. Pyrimidines / 183 4.10.4. Five-Membered Ring Heterocycles with Two Hetero Atoms: Imidazoles, Benzimidazoles, 1H-pyrazoles, Oxazoles, Isoxazoles, Thiazoles, and Indazoles / 183 4.10.5. Five-Membered Ring Heterocycles with Three or More Heteroatoms: Sydnones, Triazoles, and Benzotriazoles / 183 4.10.6. Various Other Difluoromethyl-Substituted Heterocyclic Systems / 185 5 THE TRIFLUOROMETHYL GROUP 187 5.1. Introduction / 187 5.1.1. NMR Spectra of Compounds Containing the CF3 Group – General Considerations / 187 5.2. Saturated Hydrocarbons Bearing a CF3 Group / 189 5.2.1. Alkanes Bearing a CF3 Group / 189 5.2.2. Cycloalkanes Bearing a CF3 Group / 189 5.2.3. 1H and 13C NMR Data, General Information / 191 5.3. Influence of Substituents and Functional Groups / 193 5.3.1. Impact of Halogens / 193 5.3.2. Ethers, Alcohols, Esters, Sulfides, and Selenides / 195 5.3.3. Sulfones, Sulfoxides, and Sulfoximines / 200 5.3.4. Amines and Nitro Compounds / 200 5.3.5. Trifluoromethyl Imines, Oximes, Hydrazones, Imidoyl Chlorides, Nitrones, Diazo and Diazirine Compounds / 204 5.3.6. Phosphines and Phosphonium Compounds / 205 5.3.7. Organometallics / 205 5.4. Boronic Esters / 207 5.5. Carbonyl Compounds / 207 5.5.1. 1H and 13C NMR Data / 209 5.6. Nitriles / 213 5.6.1. 13C NMR Data for Nitriles / 213 5.7. Bifunctional Compounds / 214 5.8. Sulfonic Acid Derivatives / 214 5.9. Allylic and Propargylic Trifluoromethyl Groups / 214 5.9.1. Allylic Trifluoromethyl Groups / 215 5.9.2. α,β-Unsaturated Carbonyl Compounds / 219 5.9.3. More Heavily Fluorinated Allylics / 222 5.9.4. Propargylic Trifluoromethyl Groups / 222 5.10. Aryl-Bound Trifluoromethyl Groups / 223 5.10.1. Proton and Carbon NMR Data / 224 5.10.2. Multitrifluoromethylated Benzenes / 225 5.11. Heteroaryl-Bound Trifluoromethyl Groups / 228 5.11.1. Pyridines, Quinolines, and Isoquinolines / 228 5.11.2. Pyrimidines and Quinoxalines / 229 5.11.3. Pyrroles and Indoles / 229 5.11.4. Thiophenes and Benzothiophenes / 230 5.11.5. Furans / 230 5.11.6. Imidazoles and Benzimidazoles / 232 5.11.7. Oxazoles, Isoxazoles, Oxazolidines, Thiazoles, 1H-pyrazoles, 1H-indazoles, Benzoxazoles, and Benzothiazoles / 234 5.11.8. Triazoles and Tetrazoles / 235 6 MORE HIGHLY FLUORINATED GROUPS 237 6.1. Introduction / 237 6.2. The 1,1,2- and 1,2,2-Trifluoroethyl Groups / 238 6.3. The 1,1,2,2-Tetrafluoroethyl and 2,2,3,3-Tetrafluoropropyl Groups / 241 6.4. The 1,2,2,2-Tetrafluoroethyl Group / 242 6.5. The Pentafluoroethyl Group / 245 6.5.1. Pentafluoroethyl Carbinols / 248 6.5.2. Pentafluoroethyl Ethers, Sulfides, and Phosphines / 248 6.5.3. Pentafluoroethyl Organometallics / 249 6.6. The 2,2,3,3,3-Pentafluoropropyl Group / 249 6.7. The 1,1,2,3,3,3-Hexafluoropropyl Group / 251 6.8. 1,1,2,2,3,3-Hexafluoropropyl System / 252 6.9. The Hexafluoro-Isopropyl Group / 254 6.10. The Heptafluoro-n-Propyl Group / 255 6.11. The Heptafluoro-iso-Propyl Group / 255 6.12. The Nonafluoro-n-Butyl Group / 255 6.13. The Nonafluoro-iso-Butyl Group / 258 6.14. The Nonafluoro-t-Butyl Group / 258 6.15. Fluorous Groups / 258 6.16. 1-Hydro-Perfluoroalkanes / 259 6.17. Perfluoroalkanes / 260 6.18. Perfluoro-n-Alkyl Halides / 263 6.19. Perfluoroalkyl Amines, Ethers, and Carboxylic Acid Derivatives / 263 6.20. Polyfluoroalkenes / 264 6.20.1. Trifluorovinyl Groups / 264 6.20.2. Perfluoroalkenes / 267 6.21. Polyfluorinated Aromatics / 268 6.21.1. 2,3,5,6-Tetrafluorobenzene Compounds / 268 6.21.2. The Pentafluorophenyl Group / 268 6.22. Polyfluoroheterocyclics / 269 6.22.1. Polyfluoropyridines / 269 6.22.2. Polyfluorofurans / 269 6.22.3. Polyfluorothiophenes / 269 6.22.4. Polyfluoropyrimidines / 271 7 COMPOUNDS AND SUBSTITUENTS WITH FLUORINE DIRECTLY BOUND TO A HETEROATOM 273 7.1. Introduction / 273 7.2. Boron Fluorides / 275 7.3. Fluorosilanes / 275 7.4. Nitrogen Fluorides / 275 7.4.1. Electrophilic Fluorinating Agents / 276 7.5. Phosphorous Fluorides / 277 7.5.1. Phosphorous (III) Fluorides / 277 7.5.2. Phosphorous (V) Fluorides / 277 7.5.3. Phosphorous (V) Oxyfluorides / 280 7.5.4. Cyclophosphazenes / 280 7.6. Oxygen Fluorides (Hypofluorites) / 281 7.7. Sulfur Fluorides / 282 7.7.1. Inorganic Sulfur, Selenium, and Tellurium Fluorides / 282 7.7.2. Diarylsulfur, Selenium, and Tellurium Difluorides / 282 7.7.3. Aryl and Alkyl SF3 Compounds / 283 7.7.4. Dialkylaminosulfur Trifluorides / 283 7.7.5. Hypervalent Sulfur Fluorides / 284 7.7.6. Related Hypervalent Selenium and Tellurium Fluorides / 287 7.7.7. Organic Sulfinyl and Sulfonyl Fluorides / 288 7.8. The Pentafluorosulfanyl (SF5) Group in Organic Chemistry / 289 7.8.1. Saturated Aliphatic Systems / 292 7.8.2. Vinylic SF5 Substituents / 294 7.8.3. Acetylenic SF5 Substituents / 296 7.8.4. Aromatic SF5 Substituents / 297 7.8.5. Heterocyclic SF5 Compounds / 302 7.9. Bromine Trifluoride, Iodine Trifluoride, and Iodine Pentafluoride / 304 7.10. Aryl and Alkyl Halogen Difluorides and Tetrafluorides / 304 7.11. Xenon Fluorides / 305 INDEX 307
£93.56
John Wiley & Sons Inc Organic Reactions Volume 83
Book SynopsisThe two chapters in Volume 83 describe reactions that represent two major (and growing) franchises in the Organic Reactions series, namely, transition metal catalyzed cross-coupling reactions and multicomponent reactions. These two processes not only have a rich history in synthetic organic chemistry, but also represent some of the most commonly employed transformations in the modern practice of molecule construction. The first chapter authored by Eiichi Nakamura, Takuji Hatakeyama, Shingo Ito, Kentaro Ishizuka, Laurean Ilies, and Masaharu Nakamura describes one of the most exiting advances in the field of transition metal catalyzed cross-coupling reactions: the use of iron catalysts. The second chapter authored by Stephen G. Pyne and Minyan Tang describes the latest in a long line of multicomponent reactions published in this series: the boronic acid Mannich reaction, sometimes called the Petasis reaction.Table of ContentsCHAPTER PAGE 1. IRON-CATALYZED CROSS-COUPLING REACTIONS Eiichi Nakamura, Takuji Hatakeyama, Shingo Ito, Kentaro Ishizuka, Lauren Ilies, and Masaharu Nakamura 1 2. THE BORONIC ACID MANNICH REACTION Stephen G. Pyne and Minyan Tang 211 CUMULATIVE CHAPTER TITLES BY VOLUME 499 AUTHOR INDEX, VOLUMES 1–83 515 CHAPTER AND TOPIC INDEX, VOLUMES 1–83 521
£133.20
John Wiley & Sons Inc Organic Reactions Volume 84
Book SynopsisThe two chapters in Volume 84 describe transition metal catalyzed processes that form carbon-carbon bonds and carbon-oxygen bonds in very interesting and practical ways. The first chapter authored by Christina Moberg describes an important subset of one of the earliest and most important enantioselective carbon-carbon bond forming reactions that employ transition metal complexes, namely molybdenum-catalyzed, asymmetric allylic alkylations. The second chapter authored by Brian W. Michel, Laura D. Steffens, and Matthew S. Sigman deals with one of the oldest examples of transition metal catalyzed oxidation, known as the Wacker process.Table of Contents1. Molybdenum-Catalyzed Asymmetric Allylic Alkylations Christina Moberg 1 2. The Wacker Oxidation Brian W. Michel, Laura D. Steffens, and Matthew S. Sigman 75 Cumulative Chapter Titles by Volume 415 Author Index, Volumes 1–84 431 Chapter and Topic Index, Volumes 1–84 437
£128.70
John Wiley & Sons Inc Organic Redox Systems
Book SynopsisProviding a thorough overview of leading research from internationally-recognized contributing authors, this book describes methods for the preparation and application of redox systems for organic electronic materials like transistors, photovoltaics, and batteries. Covers bond formation and cleavage, supramolecular systems, molecular design, and synthesis and properties Addresses preparative methods, unique structural features, physical properties, and material applications of redox active p-conjugated systems Offers a useful guide for both academic and industrial chemists involved with organic electronic materials Focuses on the transition-metal-free redox systems composed of organic and organo main group compounds Table of ContentsLIST OF CONTRIBUTO RS xv PREFACE xix 1 Introduction: Basic Concepts and a Brief History of Organic Redox Systems 1Tohru Nishinaga 1.1 Redox Reaction of Organic Molecules, 1 1.2 Redox Potential in Nonaqueous Solvents, 3 1.3 A Brief History of Organic Redox Compounds, 5 References, 10 2 Redox©\Mediated Reversible 𝞂©\Bond Formation/Cleavage 13Takanori Suzuki, Hitomi Tamaoki, Jun©\ichi Nishida, Hiroki Higuchi, Tomohiro Iwai, Yusuke Ishigaki, Keisuke Hanada, Ryo Katoono, Hidetoshi Kawai, Kenshu Fujiwara and Takanori Fukushima 2.1 Dynamic Redox (“Dyrex”) Systems, 13 2.1.1 π©\Electron Systems Exhibiting Drastic Structural Changes upon Electron Transfer, 13 2.1.2 Redox Switching of a σ©\Bond upon Electron Transfer, 16 2.1.3 Two Types of Dyrex Systems Exhibiting Redox Switching of a σ©\Bond, 17 2.2 Advanced Electrochromic Response of “Endo”©\Type Dyrex Systems Exhibiting Redox Switching of a σ©\Bond, 19 2.2.1 Tetraaryldihydrophenanthrenes as Prototypes of “Endo”©\Dyrex Systems, 19 2.2.2 Tricolor Electrochromism with Hysteretic Color Change in Non©\C2©\Symmetric “Endo”©\Dyrex Pair, 20 2.2.3 Electrochromism with Chiroptical Output of Chiral “Endo”©\Dyrex Pair, 21 2.2.4 Multi©\Output Response System Based on Electrochromic “Endo”©\Dyrex Pair, 24 2.3 Advanced Electrochromic Response of “Exo”©\Type Dyrex Systems Exhibiting Redox Switching of a σ©\Bond, 26 2.3.1 Bis(diarylethenyl)biphenyls as Prototypes of “Exo”©\Dyrex Systems, 26 2.3.2 Electrochromism with Chiroptical Output of Chiral “Exo”©\Dyrex Systems, 26 2.3.3 Electrochromism of “Exo”©\Dyrex Systems in Aqueous Media, 28 2.4 Prospect: Redox Systems With Multiple Dyrex Units, 31 References, 33 3 Redox©\Controlled Intramolecular Motions Triggered by π©\Dimerization and Pimerization Processes 39Christophe Kahlfuss, Eric Saint©\Aman and Christophe Bucher 3.1 Introduction, 39 3.2 Oligothiophenes, 40 3.3 Phenothiazine, 44 3.4 Naphthalene and Perylene Bisimides, 45 3.5 para©\Phenylenediamine, 47 3.6 Pyridinyl Radicals, 49 3.7 Viologen Derivatives, 50 3.8 Verdazyl, 60 3.9 Phenalenyl, 60 3.10 Porphyrins, 61 3.11 Benzenoid, 62 3.12 Cyclophane, 64 3.13 Tetrathiafulvalene, 68 3.14 Conclusion, 80 Acknowledgments, 80 References, 81 4 Tetrathiafulvalene: a Redox Unit for Functional Materials and a Building Block for Supramolecular Self©\Assembly 89Masashi Hasegawa and Masahiko Iyoda 4.1 Introduction: Past and Present of TTF Chemistry, 89 4.2 Basic Redox Properties of TTF and Stacked TTF, 90 4.2.1 Monomeric TTFs, 90 4.2.2 Interactions in Stacked TTF Dimer, 92 4.2.3 Interactions in Stacked TTF Oligomers, 97 4.2.4 Head©\to©\Tail TTF Dimer, 98 4.3 TTF as a Faithful Redox Active Unit in Functional Materials, 100 4.3.1 Electrochromic Materials, 100 4.3.2 Optically Active TTFs, 102 4.3.3 Uses as Positive Electrode Materials for Rechargeable Batteries, 108 4.4 Electroconducting Properties of TTF Derivatives Based on Supramolecular Self©\Assembly, 112 4.4.1 Redox©\Active Nanostructure Formation in the Solid State, 113 4.4.2 Conducting Nanostructure Formation, 115 4.4.3 Conducting Nanofibers by Iodine Doping, 116 4.4.4 Conducting Nanofibers Based on Cation Radicals, 120 4.4.5 Conducting Nanowires of Neutral TTF Derivatives, 123 4.5 Summary and Outlook, 124 References, 125 5 Robust Aromatic Cation Radicals as Redox Tunable Oxidants 131Marat R. Talipov and Rajendra Rathore 5.1 Introduction, 131 5.2 Designing Molecules for the Formation of Stable Cation Radicals (Crs)—A Case Study, 135 5.2.1 Exploring the Cause of Exceptional Stability of The©\Orange+·, 137 5.3 Methods of Preparative Isolation of Aromatic Cation Radicals, 142 5.3.1 Nitrosonium (NO+) Salts, 143 5.3.2 Antimony Pentachloride (SbCl5), 144 5.3.3 Triethyloxonium Hexachloroantimonate (Et3O+ SbCl6 –), 148 5.3.4 Ddq and HBF4©\Ether Complex, 149 5.4 Q uantitative Oxidation of Electron Donors using THE-Orange+·SbCl6 – as One©\Electron Oxidant, 150 5.4.1 Analysis of Two©\Electron Oxidation Processes Using MF/D Plots, 157 5.5 Readily Available Electron Donors for the Redox©\Tunable Aromatic Oxidants, 164 5.5.1 Triptycene Based Electron Donors, 164 5.5.2 Tetrabenzodifurans, 166 5.5.3 Polyaromatic Hydrocarbons, 168 5.5.4 Multi©\Electron Redox Systems, 168 5.6 Conclusion, 171 References, 173 6 Air©\Stable Redox©\Active Neutral Radicals: Topological Symmetry Control of Electronic©\Spin, Multicentered Chemical Bonding, and Organic Battery Application 177Shinsuke Nishida and Yasushi Morita 6.1 Introduction, 177 6.2 Open©\Shell Graphene Fragment : Design and Synthesis of Air©\Stable Carbon©\Centered Neutral Radicals Based on Fused©\Polycyclic π©\System, 179 6.3 Topological Symmetry Control of Electronic©\Spin Density Distribution by Redox and other External Stimuli, 181 6.3.1 Redox©\Based Spin Diversity of Oxophenalenoxyl Sytems, 181 6.3.2 Spin©\Center Transfer and Solvato©\/Thermochromism of Tetrathiafulvalene©\Substituted 6©\Oxophenalenoxyl Neutral Radical, 183 6.4 Control of Electronic©\Spin Structure and Optical Properties of Multicentered C©¤C Bonds, 184 6.4.1 Strong Somo–Somo Interaction within π©\Dimeric Structure of Phenalenyl Derivatives, 184 6.4.2 Thermochromism Induced by Thermal Equilibrium of π©\Dimeric Structure and σ©\Dimeric Structure, 188 6.4.3 Weak Somo–Somo Interactions by Molecular Modification of Phenalenyl System, 190 6.4.4 Multidimensional Spin–Spin Interaction and π©\Staked Radical Polymer, 193 6.5 Rechargeable Batteries Using Organic Electrode©\Active Materials, 195 6.5.1 Closed©\Shell Organic Molecules as Electrode©\Active Materials, 196 6.5.2 Closed©\Shell Organic Polymers, 214 6.5.3 Stable Organic Neutral Radicals, 218 6.5.4 Stable Organic Neutral Radical Polymers, 220 6.6 Molecular Spin Batteries : Design Criteria and Performance of High Capacity Organic Rechargeable Battery Materials, 223 6.6.1 Molecular Crystalline Secondary Batteries, 223 6.6.2 Trioxotriangulene Neutral Radical (Tot) Derivatives, 224 6.6.3 Molecular Spin Batteries, 227 6.7 Conclusion, 229 Acknowledgement, 231 References, 231 7 Triarylamine©\Based Organic Mixed©\Valence Compounds: The Role of the Bridge 245Christoph Lambert 7.1 Introduction, 245 7.2 The Mv Concept, 246 7.3 The Redox Center, 250 7.4 The Bridge, 251 7.5 The Length of the Bridge, 254 7.6 Changing the Connectivity, 256 7.7 Twisting the Bridge, 258 7.8 Saturated vs Unsaturated Bridge, 258 7.9 Meta vs Para Conjugation, 260 7.10 Switching the Bridge, 262 7.11 Metal Atoms as the Bridge, 263 7.12 And Finally: Without a Bridge, 264 Acknowledgment, 265 References, 265 8 Magnetic Properties of Multiradicals Based on Triarylamine Radical Cations 269Shuichi Suzuki and Keiji Okada 8.1 Introduction, 269 8.2 Triarylamine Radical Cations as Synthetic Reagents for Preparation of Donor Radical Cations with Various Counter Anions, 270 8.2.1 Syntheses of Tbpa +·Pf6− and Its Counteranion Analogues, 270 8.3 Stable Triarylamines without para©\Substituents, 270 8.4 Models of Intermolecular Exchange Interaction in Heteroatomic Systems, 271 8.4.1 Dynamic Spin Polarization Model and Disjoint–Nondisjoint Model, 271 8.4.2 Dynamic Spin Polarization and Spin Delocalization, 272 8.4.3 Effect of Large Dihedral Angle between Spacer and Spin Source, 273 8.4.4 p©\Phenylene Methodology or π©\Conjugation Using Topologically Different Spin Sources, 275 8.5 Magnetic Susceptibility and Temperature Dependence, 275 8.6 Poly(Diarylamino benzene) Poly(Radical Cation)s, 276 8.7 Radical Substituted Triarylamines, 278 8.7.1 tbuno©\Substituted Triarylamines, 278 8.7.2 Nn©\Substituted Triarylamines, 279 8.8 Towards Further Developments, 282 References, 283 9 Open©\Shell π©\Conjugated Hydrocarbons 287Takashi Kubo 9.1 Introduction, 287 9.2 Monoradicals, 288 9.2.1 Triphenylmethyl, 288 9.2.2 Phenalenyl, 289 9.2.3 Cyclopentadienyl, Indenyl, Fluorenyl, 291 9.2.4 Cycloheptatrienyl, 293 9.2.5 Bdpa , 294 9.2.6 Dinaphthofluorenyl, 294 9.3 Biradicals, 295 9.3.1 Triplet Biradicals, 295 9.3.2 Singlet Biradicals: Quinodimethanes, 296 9.3.3 Singlet Biradicals: Bisphenalenyl System, 298 9.3.4 Singlet Biradicals: Acences, 300 9.3.5 Singlet Biradicals: Anthenes, 301 9.3.6 Singlet Biradicals: Zethrenes, 303 9.3.7 Singlet Biradicals: Indenofluorenes, 304 9.4 Polyradicals, 304 References, 305 10 Indenofluorenes and Related Structures 311Jonathan L. Marshall and Michael M. Haley 10.1 Introduction, 311 10.2 Indeno[1,2©\a]fluorenes, 313 10.2.1 Indeno[1,2©\a]fluorene©\7,12©\dione, 313 10.2.2 Truxenone, An Indeno[1,2©\a]fluorene Related Structure, 314 10.3 Indeno[1,2©\b]fluorenes, 320 10.3.1 Indeno[1,2©\b]fluorene©\6,12©\diones, 320 10.3.2 Dicyanomethylene Indeno[1,2©\b]fluorenes, 325 10.3.3 Fully Conjugated Indeno[1,2©\b]fluorenes, 327 10.4 Indeno[2,1©\a]fluorenes, 333 10.5 Indeno[2,1©\b]fluorenes, 336 10.6 Indeno[2,1©\c]fluorenes, 339 10.6.1 Indenofluorene-Related Structures, 341 10.7 Fluoreno[4,3©\c]fluorene, 342 10.8 Indacenedithiophenes, 345 10.8.1 Indacenedithiophene Diones, 345 10.8.2 Tetrathiofulvalene and Dicyanomethylene Indacenedithiophenes, 347 10.8.3 Fully Conjugated Indacenedithiophenes, 349 10.9 Diindeno[n]thiophenes, 351 10.10 Conclusions, 354 Acknowledgment, 354 References, 354 11 Thienoacenes 359Kazuo Takimiya 11.1 Introduction, 359 11.2 Synthesis of Thienoacenes via Thienannulation, 361 11.2.1 Bdt and Adt Derivatives, 361 11.2.2 Thienannulation to Construct Thienoacenes with Terminal Thiophene Ring(s), 362 11.2.3 Thienannulation to Construct Thienoacenes with Internal Thiophene Ring(s), 366 11.3 Molecular Electronic Structures, 370 11.4 Application to Electronic Devices, 373 11.4.1 Molecular Organic Semiconductors for p©\Type OFET Devices, 373 11.4.2 Semiconducting Polymers for Pscs, 377 11.5 Summary, 379 References, 379 12 Cationic Oligothiophenes: p©\Doped Polythiophene Models and Applications 383Tohru Nishinaga 12.1 Introduction, 383 12.2 Design Principle and Synthetic Methods, 384 12.3 Electrochemistry, 390 12.4 Structural and Spectroscopic Properties as p©\Doped Polythiophene Models, 397 12.5 Application to Supramolecular Systems, 403 12.6 Conclusion and Outlook, 406 References, 406 13 Electron©\Deficient Conjugated Heteroaromatics 411Yutaka Ie and Yoshio Aso 13.1 Introduction, 411 13.2 Hexafluorocyclopenta[c]thiophene and its Containing Oligothiiophenes, 412 13.3 Difluoromethylene©\Bridged Bithiophene and its Containing Oligothiiophenes, 416 13.4 π©\Conjugated Systems Having Thiazole©\Based Carbonyl©\Bridged Compounds, 419 13.5 Difluorodioxocyclopentene©\Annelated Thiophene and its Containing Oligothiiophenes, 427 13.6 Dioxocycloalkene©\Annelated Thiophene and its Containing Oligothiiophenes, 433 13.7 Dicyanomethylene©\Substituted Cyclopenta[b]thiophene and its Containing π©\Conjugated System, 434 13.8 Electron©\Deficient π©\Conjugated System Containing Dicyanomethylene©\Substituted Cyclopenta[b]thiophene Toward Organic Photovoltaics, 437 13.9 Conclusion, 440 References, 441 14 Oligofurans 445Ori Gidron 14.1 Background, 445 14.2 Synthesis and Reactivity, 446 14.3 Properties of Oligofurans in the Neutral State, 449 14.4 Properties of Cationic Oligofurans, 452 14.5 Polyfurans, 454 14.6 Devices with Furan©\Containing Materials, 455 14.7 Summary and Outlook, 459 References, 459 15 Oligopyrroles and Related Compounds 463Masayoshi Takase 15.1 Introduction, 463 15.2 Linear Oligopyrroles, 464 15.2.1 Synthesis, 464 15.2.2 Optical and Redox Properties, 465 15.2.3 π©\Dimer of Oligopyrrole Radical Cations, 466 15.3 Cyclic Oligopyrroles, 467 15.3.1 Synthesis, 468 15.3.2 Optical and Redox Properties, 469 15.4 Pyrrole©\Fused Azacoronenes, 469 15.4.1 Synthesis, 470 15.4.2 Optical and Redox Properties, 470 15.4.3 Aromaticity, 473 15.5 Conclusions, 474 References, 474 16 Phospholes and Related Compounds: Syntheses, Redox Properties, and Applications to Organic Electronic Devices 477Yoshihiro Matano 16.1 Introduction, 477 16.2 Synthesis of π©\Conjugated Phosphole Derivatives, 478 16.3 Redox Potentials of Phosphole Derivatives, 483 16.4 Electrochemical Behaviors of Phosphole Derivatives, 493 16.5 Applications of Phosphole©\Based Materials to Organic Electronic Devices, 495 References, 497 17 Electrochemical Behavior and Redox Chemistry of Boroles 503Holger Braunschweig and Ivo Krummenacher 17.1 Introduction, 503 17.2 Preparation, 505 17.3 Chemical Reactivity, 507 17.3.1 Lewis Acid–Base Adducts, 507 17.3.2 Cycloaddition Reactions, 508 17.3.3 σ©\Bond Activation Reactions, 509 17.4 Redox Chemistry, 510 17.4.1 Electrochemistry, 510 17.4.2 Preparative Reduction Chemistry, 514 17.5 Conclusions and Outlook, 518 References, 519 18 Isolation and Crystallization of Radical Cations by Weakly Coordinating Anions 523Xinping Wang 18.1 Introduction, 523 18.2 Radical Cations and Dications Based on Triarylamines, 524 18.3 Radical Cations Containing Phosphorus, 528 18.4 The Radical Cation Containing a Selenium–Selenium Three©\Electron σ©\Bond, 534 18.5 Radical Cations of Organic Oligomers (π©\Dimerization), 536 18.6 σ©\Dimerization of Radical Cations, 540 18.7 Conclusion, 541 References, 542 19 Heavier Group 14 Element Redox Systems 545Vladimir Ya. Lee and Akira Sekiguchi 19.1 Introduction, 545 19.2 Redox Systems of the Heavier Group 14 Elements E (E = Si–Pb), 547 19.2.1 Interconversion between Cations R3E+, Radicals R3E ·, and Anions R3E−, 547 19.2.2 Anion and Cation©\Radicals of the Heavy Analogs of Carbenes R2E:, 552 19.2.3 Anion©\ and Cation©\Radicals of the Heavy Analogs of Alkenes R2E¨TER2 and Heavy Analogs of Alkynes R©¤E≡E©¤R, 555 19.3 Summary, 559 References, 559 20 π©\Electron Redox Systems of Heavier Group 15 Elements 563Takahiro Sasamori, Norihiro Tokitoh and Rainer Streubel 20.1 Introduction, 563 20.2 The Redox Behavior of Dipnictenes, 564 20.3 The Redox Behavior of π©\Conjugated Systems of Heavier Dipnictenes, 571 20.4 The Redox Behavior of d–π Electron Systems Containing Heavier Dipnictenes, 572 20.5 Conclusion, 575 References, 575 Index 579
£152.06
John Wiley & Sons Inc Lipidomics
Book SynopsisCovers the area of lipidomics from fundamentals and theory to applications Presents a balanced discussion of the fundamentals, theory, experimental methods and applications of lipidomics Covers different characterizations of lipids including Glycerophospholipids; Sphingolipids; Glycerolipids and Glycolipids; and Fatty Acids and Modified Fatty Acids Includes a section on quantification of Lipids in Lipidomics such as sample preparation; factors affecting accurate quantification; and data processing and interpretation Details applications of Lipidomics Tools including for Health and Disease; Plant Lipidomics; and Lipidomics on Cellular Membranes Table of ContentsForeword xix Preface xxi Abbreviations xxv Part I Introduction 1 1 Lipids and Lipidomics 3 1.1 Lipids, 3 1.1.1 Definition, 3€ 1.1.2 Classification, 4 1.1.2.1 Lipid MAPS Approach, 7 1.1.2.2 Building Block Approach, 10 1.2 Lipidomics, 13 1.2.1 Definition, 13 1.2.2 History of Lipidomics, 14 References, 16 2 Mass Spectrometry for Lipidomics 21 2.1 Ionization Techniques, 21 2.1.1 Electrospray Ionization, 22 2.1.1.1 Principle of Electrospray Ionization, 22 2.1.1.2 Features of Electrospray Ionization for Lipid Analysis, 28 2.1.1.3 Advent of ESI for Lipid Analysis: Nano-ESI and Off-Axis Ion Inlets, 30 2.1.2 Matrix-Assisted Laser Desorption/Ionization, 30 2.2 Mass Analyzers, 32 2.2.1 Quadrupole, 32 2.2.2 Time of Flight, 33 2.2.3 Ion Trap, 35 2.3 Detector, 36 2.4 Tandem Mass Spectrometry Techniques, 37 2.4.1 Product-Ion Analysis, 37 2.4.2 Neutral-Loss Scan, 39 2.4.3 Precursor-Ion Scan, 39 2.4.4 Selected Reaction Monitoring, 39 2.4.5 Interweaving Tandem Mass Spectrometry Techniques, 40 2.5 Other Recent Advances in Mass Spectrometry for Lipid Analysis, 42 2.5.1 Ion-Mobility Mass Spectrometry, 43 2.5.2 Desorption Electrospray Ionization, 43 References, 45 3 Mass Spectrometry-Based Lipidomics Approaches 53 3.1 Introduction, 53 3.2 Shotgun Lipidomics: Direct Infusion-Based Approaches, 54 3.2.1 Devices for Direct Infusion, 54 3.2.2 Features of Shotgun Lipidomics, 55 3.2.3 Shotgun Lipidomics Approaches, 56 3.2.3.1 Tandem Mass Spectrometry-Based Shotgun Lipidomics, 56 3.2.3.2 High Mass Accuracy-Based Shotgun Lipidomics, 56 3.2.3.3 Multidimensional MS-Based Shotgun Lipidomics, 57 3.2.4 Advantages and Drawbacks, 63 3.2.4.1 Tandem Mass Spectrometry-Based Shotgun Lipidomics, 63 3.2.4.2 High Mass Accuracy-Based Shotgun Lipidomics, 63 3.2.4.3 Multidimensional Mass Spectrometry-Based Shotgun Lipidomics, 64 3.3 LC-MS-Based Approaches, 65 3.3.1 General, 65 3.3.1.1 Selected Ion Monitoring for LC-MS, 66 3.3.1.2 Selected/Multiple Reaction Monitoring for LC-MS, 67 3.3.1.3 Data-Dependent Analysis after LC-MS, 67 3.3.2 LC-MS-Based Approaches for Lipidomics, 68 3.3.2.1 Normal-Phase LC-MS-Based Approaches, 68 3.3.2.2 Reversed-Phase LC-MS-Based Approaches, 69 3.3.2.3 Hydrophilic Interaction LC-MS-Based Approaches, 71 3.3.2.4 Other LC-MS-Based Approaches, 72 3.3.3 Advantages and Drawbacks, 72 3.3.4 Identification of Lipid Species after LC-MS, 73 3.4 MALDI-MS for Lipidomics, 74 3.4.1 General, 74 3.4.2 Analysis of Lipid Extracts, 74 3.4.3 Advantages and Drawbacks, 75 3.4.4 Recent Advances in MALDI-MS for Lipidomics, 76 3.4.4.1 Utilization of Novel Matrices, 76 3.4.4.2 (HP)TLC-MALDI-MS, 78 3.4.4.3 Matrix-Free Laser Desorption/Ionization Approaches, 78 References, 79 4 Variables in Mass Spectrometry for Lipidomics 89 4.1 Introduction, 89 4.2 Variables in Lipid Extraction (i.e., Multiplex Extraction Conditions), 89 4.2.1 The pH Conditions of Lipid Extraction, 89 4.2.2 Solvent Polarity of Lipid Extraction, 90 4.2.3 Intrinsic Chemical Properties of Lipids, 90 4.3 Variables in the Infusion Solution, 91 4.3.1 Polarity, Composition, Ion Pairing, and Other Variations in the Infusion Solution, 91 4.3.2 Variations of the Levels or Composition of a Modifier in the Infusion Solution, 93 4.3.3 Lipid Concentration in the Infusion Solution, 97 4.4 Variables in Ionization, 98 4.4.1 Source Temperature, 98 4.4.2 Spray Voltage, 99 4.4.3 Injection/Eluent Flow Rate, 100 4.5 Variables in Building-Block monitoring with MS/MS Scanning, 102 4.5.1 Precursor-Ion Scanning of a Fragment Ion Whose m/z Serves as a Variable, 102 4.5.2 Neutral-Loss Scanning of a Neutral Fragment Whose Mass Serves as a Variable, 102 4.5.3 Fragments Associated with the Building Blocks are the Variables in Product-Ion MS Analysis, 103 4.6 Variables in Collision, 104 4.6.1 Collision Energy, 104 4.6.2 Collision-Gas Pressure, 104 4.6.3 Collision Gas Type, 108 4.7 Variables in Separation, 108 4.7.1 Charge Properties in Intrasource Separation, 108 4.7.2 Elution Time in LC Separation, 111 4.7.3 Matrix Properties in Selective Ionization by MALDI, 112 4.7.4 Drift Time (or Collision Cross Section) in Ion-Mobility Separation, 112 4.8 Conclusion, 114 References, 114 5 Bioinformatics in Lipidomics 121 5.1 Introduction, 121 5.2 Lipid Libraries and Databases, 122 5.2.1 Lipid MAPS Structure Database, 122 5.2.2 Building-Block Concept-Based Theoretical Databases, 123 5.2.3 LipidBlast – in silico Tandem Mass Spectral Library, 129 5.2.4 METLIN Database, 130 5.2.5 Human Metabolome Database, 131 5.2.6 LipidBank Database, 131 5.3 Bioinformatics Tools in Automated Lipid Data Processing, 132 5.3.1 LC-MS Spectral Processing, 132 5.3.2 Biostatistical Analyses and Visualization, 134 5.3.3 Annotation for Structure of Lipid Species, 135 5.3.4 Software Packages for Common Data Processing, 136 5.3.4.1 XCMS, 136 5.3.4.2 MZmine 2, 136 5.3.4.3 A Practical Approach for Determination of Mass Spectral Baselines, 137 5.3.4.4 LipidView, 137 5.3.4.5 LipidSearch, 137 5.3.4.6 SimLipid, 138 5.3.4.7 MultiQuant, 139 5.3.4.8 Software Packages for Shotgun Lipidomics, 139 5.4 Bioinformatics for Lipid Network/Pathway Analysis and Modeling, 139 5.4.1 Reconstruction of Lipid Network/Pathway, 139 5.4.2 Simulation of Lipidomics Data for Interpretation of Biosynthesis Pathways, 140 5.4.3 Modeling of Spatial Distributions and Biophysical 5.5 Integration of "Omics", 143 5.5.1 Integration of Lipidomics with Other Omics, 143 5.5.2 Lipidomics Guides Genomics Analysis, 144 References, 145 Part II Characterization of Lipids 151 6 Introduction 153 6.1 Structural Characterization for Lipid Identification, 153 6.2 Pattern Recognition for Lipid Identification, 157 6.2.1 Principles of Pattern Recognition, 157 6.2.2 Examples, 159 6.2.2.1 Choline Lysoglycerophospholipid, 159 6.2.2.2 Sphingomyelin, 161 6.2.2.3 Triacylglycerol, 164 6.2.3 Summary, 169 References, 170 7 Fragmentation Patterns of Glycerophospholipids 173 7.1 Introduction, 173 7.2 Choline Glycerophospholipid, 175 7.2.1 Positive Ion Mode, 175 7.2.1.1 Protonated Species, 175 7.2.1.2 Alkaline Adducts, 175 7.2.2 Negative-Ion Mode, 178 7.3 Ethanolamine Glycerophospholipid, 180 7.3.1 Positive-Ion Mode, 180 7.3.1.1 Protonated Species, 180 7.3.1.2 Alkaline Adducts, 180 7.3.2 Negative-Ion Mode, 182 7.3.2.1 Deprotonated Species, 182 7.3.2.2 Derivatized Species, 183 7.4 Phosphatidylinositol and Phosphatidylinositides, 184 7.4.1 Positive-Ion Mode, 184 7.4.2 Negative-Ion Mode, 184 7.5 Phosphatidylserine, 185 7.5.1 Positive-Ion Mode, 185 7.5.2 Negative-Ion Mode, 186 7.6 Phosphatidylglycerol, 186 7.6.1 Positive-Ion Mode, 186 7.6.2 Negative-Ion Mode, 186 7.7 Phosphatidic Acid, 187 7.7.1 Positive-Ion Mode, 187 7.7.2 Negative-Ion Mode, 188 7.8 Cardiolipin, 188 7.9 Lysoglycerophospholipids, 190 7.9.1 Choline Lysoglycerophospholipids, 190 7.9.2 Ethanolamine Lysoglycerophospholipids, 191 7.9.3 Anionic Lysoglycerophospholipids, 193 7.10 Other Glycerophospholipids, 193 7.10.1 N-Acyl Phosphatidylethanolamine, 193 7.10.2 N-Acyl Phosphatidylserine, 194 7.10.3 Acyl Phosphatidylglycerol, 194 7.10.4 Bis(monoacylglycero)phosphate, 194 7.10.5 Cyclic Phosphatidic Acid, 196 References, 196 8 Fragmentation Patterns of Sphingolipids 201 8.1 Introduction, 201 8.2 Ceramide, 202 8.2.1 Positive-Ion Mode, 202 8.2.2 Negative-Ion Mode, 203 8.3 Sphingomyelin, 205 8.3.1 Positive-Ion Mode, 205 8.3.2 Negative-Ion Mode, 205 8.4 Cerebroside, 205 8.4.1 Positive-Ion Mode, 205 8.4.2 Negative-Ion Mode, 207 8.5 Sulfatide, 208 8.6 Oligoglycosylceramide and Gangliosides, 208 8.7 Inositol Phosphorylceramide, 210 8.8 Sphingolipid Metabolites, 210 8.8.1 Sphingoid Bases, 210 8.8.2 Sphingoid-1-Phosphate, 212 8.8.3 Lysosphingomyelin, 212 8.8.4 Psychosine, 213 References, 213 9 Fragmentation Patterns of Glycerolipids 217 9.1 Introduction, 217 9.2 Monoglyceride, 218 9.3 Diglyceride, 218 9.4 Triglyceride, 222 9.5 Hexosyl Diacylglycerol, 223 9.6 Other Glycolipids, 224 References, 226 10 Fragmentation Patterns of Fatty Acids and Modified Fatty Acids 229 10.1 Introduction, 229 10.2 Nonesterified Fatty Acid, 230 10.2.1 Underivatized Nonesterified Fatty Acid, 230 10.2.1.1 Positive-Ion Mode, 230 10.2.1.2 Negative-Ion Mode, 230 10.2.2 Derivatized Nonesterified Fatty Acid, 233 10.2.2.1 Off-Line Derivatization, 233 10.2.2.2 Online Derivatization (Ozonolysis), 234 10.3 Modified Fatty Acid, 234 10.4 Fatty Acidomics, 238 References, 241 11 Fragmentation Patterns of other Bioactive Lipid Metabolites 243 11.1 Introduction, 243 11.2 Acylcarnitine, 244 11.3 Acyl CoA, 245 11.4 Endocannabinoids, 246 11.4.1 N-Acyl Ethanolamine, 247 11.4.2 2-Acyl Glycerol, 247 11.4.3 N-Acyl Amino Acid, 247 11.5 4-Hydroxyalkenal, 248 11.6 Chlorinated Lipids, 251 11.7 Sterols and Oxysterols, 251 11.8 Fatty Acid–Hydroxy Fatty Acids, 252 References, 253 12 Imaging Mass Spectrometry of Lipids 259 12.1 Introduction, 259 12.1.1 Samples Suitable for MS Imaging of Lipids, 260 12.1.2 Sample Processing/Preparation, 260 12.1.3 Matrix Application, 261 12.1.3.1 Matrix Application, 261 12.1.3.2 Matrix Application Methods, 262 12.1.4 Data Processing, 263 12.1.4.1 Biomap, 263 12.1.4.2 FlexImaging, 264 12.1.4.3 MALDI Imaging Team Imaging Computing System (MITICS), 264 12.1.4.4 DataCube Explorer, 264 12.1.4.5 imzML, 264 12.2 MALDI-MS Imaging, 264 12.3 Secondary-Ion Mass Spectrometry Imaging, 267 12.4 DESI-MS Imaging, 268 12.5 Ion-Mobility Imaging, 270 12.6 Advantages and Drawbacks of Imaging Mass Spectrometry for Analysis of Lipids, 270 12.6.1 Advantages, 270 12.6.2 Limitations, 272 References, 272 Part III Quantification of Lipids in Lipidomics 281 13 Sample Preparation 283 13.1 Introduction, 283 13.2 Sampling, Storage, and Related Concerns, 284 13.2.1 Sampling, 284 13.2.2 Sample Storage Prior to Extraction, 286 13.2.3 Minimizing Autoxidation, 287 13.3 Principles and Methods of Lipid Extraction, 288 13.3.1 Principles of Lipid Extraction, 289 13.3.2 Internal Standards, 292 13.3.3 Lipid Extraction Methods, 295 13.3.3.1 Folch Extraction, 295 13.3.3.2 Bligh–Dyer Extraction, 296 13.3.3.3 MTBE Extraction, 297 13.3.3.4 BUME Extraction, 298 13.3.3.5 Extraction of Plant Samples, 298 13.3.3.6 Special Cases, 298 13.3.4 Contaminants and Artifacts in Extraction, 299 13.3.5 Storage of Lipid Extracts, 300 References, 300 14 Quantification of Individual Lipid Species in Lipidomics 305 14.1 Introduction, 305 14.2 Principles of Quantifying Lipid Species by Mass Spectrometry, 308 14.3 Methods for Quantification in Lipidomics, 312 14.3.1 Tandem Mass Spectrometry-Based Method, 312 14.3.2 Two-Step Quantification Approach Used in MDMS-SL, 317 14.3.3 Selected Ion Monitoring Method, 321 14.3.4 Selected Reaction Monitoring Method, 324 14.3.5 High Mass Accuracy Mass Spectrometry Approach, 327 References, 329 15 Factors Affecting Accurate Quantification of Lipids 335 15.1 Introduction, 335 15.2 Lipid Aggregation, 336 15.3 Linear Dynamic Range of Quantification, 337 15.4 Nuts and Bolts of Tandem Mass Spectrometry for Quantification of Lipids, 339 15.5 Ion Suppression, 341 15.6 Spectral Baseline, 343 15.7 The Effects of Isotopes, 344 15.8 Minimal Number of Internal Standards for Quantification, 347 15.9 In-Source Fragmentation, 349 15.10 Quality of Solvents, 350 15.11 Miscellaneous in Quantitative Analysis of Lipids, 350 References, 350 16 Data Quality Control and Interpretation 353 16.1 Introduction, 353 16.2 Data Quality Control, 354 16.3 Recognition of Lipid Metabolism Pathways for Data Interpretation, 355 16.3.1 Sphingolipid Metabolic Pathway Network, 356 16.3.2 Network of Glycerophospholipid Biosynthesis Pathways, 356 16.3.3 Glycerolipid Metabolism, 359 16.3.4 Interrelationship between Different Lipid Categories, 360 16.4 Recognition of Lipid Functions for Data Interpretation, 360 16.4.1 Lipids Serve as Cellular Membrane Components, 360 16.4.2 Lipids Serve as Cellular Energy Storage Depots, 363 16.4.3 Lipids Serve as Signaling Molecules, 365 16.4.4 Lipids Play Other Cellular Roles, 366 16.5 Recognizing the Complication of Sample Inhomogeneity and Cellular Compartments in Data Interpretation, 368 16.6 Integration of "Omics" for Data Supporting, 369 References, 370 Part IV Applications of Lipidomics in Biomedical and Biological Research 377 17 Lipidomics for Health and Disease 379 17.1 Introduction, 379 17.2 Diabetes and Obesity, 380 17.3 Cardiovascular Diseases, 382 17.4 Nonalcohol Fatty Liver Disease, 383 17.5 Alzheimer’s disease, 385 17.6 Psychosis, 387 17.7 Cancer, 388 17.8 Lipidomics in Nutrition, 390 17.8.1 Lipidomics in Determination of the Effects of Specific Diets or Challenge Tests, 391 17.8.2 Lipidomics to Control Food Quality, 392 References, 393 18 Plant Lipidomics 405 18.1 Introduction, 405 18.2 Characterization of Lipids Special to Plant Lipidome, 406 18.2.1 Galactolipids, 407 18.2.2 Sphingolipids, 408 18.2.3 Sterols and Derivatives, 410 18.2.4 Sulfolipids, 410 18.2.5 Lipid A and Intermediates, 411 18.3 Lipidomics for Plant Biology, 411 18.3.1 Stress-Induced Changes of Plant Lipidomes, 411 18.3.1.1 Lipid Alterations in Plants Induced by Temperature Changes, 411 18.3.1.2 Wounding-Induced Alterations in Plastidic Lipids, 415 18.3.1.3 Phosphorus Deficiency-Resulted Changes of Glycerophospholipids and Galactolipids, 416 18.3.2 Changes of Plant Lipidomes during Development, 416 18.3.2.1 Alterations in Lipids during Development of Cotton Fibers, 416 18.3.2.2 Changes of Lipids during Potato Tuber Aging and Sprouting, 417 18.3.3 Characterization of Gene Function by Lipidomics, 417 18.3.3.1 Role of Fatty Acid Desaturases and DHAP Reductase in Systemic Acquired Resistance, 417 18.3.3.2 Roles of Phospholipases in Response to Freezing, 419 18.3.3.3 Role of PLDζ in Phosphorus Deficiency-Induced Lipid Changes, 419 18.3.4 Lipidomics Facilitates Improvement of Genetically Modified Food Quality, 420 References, 421 19 Lipidomics on Yeast and Mycobacterium Tuberculosis 427 19.1 Introduction, 427 19.2 Yeast Lipidomics, 428 19.2.1 Protocol for Analysis of Yeast Lipidomes by Mass Spectrometry, 428 19.2.2 Quantitative Analysis of Yeast Lipidome, 430 19.2.3 Comparative Lipidomics Studies on Different Yeast Strains, 431 19.2.4 Lipidomics of Yeast for Lipid Biosynthesis and Function, 432 19.2.5 Determining the Effects of Growth Conditions on Yeast Lipidomes, 435 19.3 Mycobacterium Tuberculosis Lipidomics, 436 References, 438 20 Lipidomics on Cell Organelle and Subcellular Membranes 443 20.1 Introduction, 443 20.2 Golgi, 444 20.3 Lipid Droplets, 445 20.4 Lipid Rafts, 447 20.5 Mitochondrion, 449 20.6 Nucleus, 452 20.7 Conclusion, 453 References, 454 Index 459
£112.46
John Wiley & Sons Inc Organic Reactions Volume 85
Book SynopsisVolume 85 represents the ninth single chapter volume to be produced in Organic Reactions'' 72-year history. The original authors, Drs. Shaughnessy and DeVasher, have compiled an enormous (and growing) literature and distilled it into an extraordinarily useful treatise on all aspects of the copper-catalyzed amination process. Given the myriad types of nitrogen-based nucleophiles and various ligand sets and reaction conditions, the authors have done an outstanding job of identifying the best options for various permutations of donor and acceptor. This comprehensive treatment of so many different options constitutes a dream field guide for the perplexed chemist who wants to know how best to approach the formation of a C-N bond in a target structure and whether copper or palladium catalysis is recommended.Table of Contents1. Copper-Catalyzed Amination of Aryl and Alkenyl Electrophiles 1 Kevin H. Shaughnessy, Engelbert Ciganek, and Rebecca B. DeVasher Cumulative Chapter Titles by Volume 669 Author Index, Volumes 1–85 685 Chapter and Topic Index, Volumes 1–85 691
£143.10
John Wiley & Sons Inc Organic Reactions Volume 87
Book SynopsisThe first chapter describes the manifold ways in which the latent functionality embedded in the humble heterocycle furan can be revealed by various oxidative processes.The second chapter details the fascinating cycloaddition and electrocyclization chemistry of unsaturated ketenes. The third chapter chronicles the development of a remarkable organometallic reaction of unactivated alkenes and alkynes, namely carbozincation.Table of Contents1. Oxidative Cleavage of FuransPedro Merino 1 2. Cycloaddition and Electrocyclic Reactions of Vinylketenes, Allenylketenes, and AlkynylketenesNanyan Fu and Thomas T. Tidwell 257 3. Carbozincation Reactions of Carbon–Carbon Multiple BondsGenia Sklute, Hannah Cavender, and Ilan Marek 507 Cumulative Chapter Titles by Volume 765 Author Index, Volumes 1–87 781 Chapter and Topic Index, Volumes 1–87 787
£138.60
John Wiley & Sons Inc Aromaticity and Antiaromaticity
Book SynopsisAromaticity and Antiaromaticity A comprehensive review of the science of aromaticity, as well as its evolution, from benzene to atomic clusters In Aromaticity and Antiaromaticity: Concepts and Applications, a team of accomplished chemists delivers a comprehensive exploration of the evolution and critical aspects of aromaticity. The book examines the new global criteria used to evaluate aromaticity, including the Nucleus Independent Chemical Shift (NICS) index and the electronic indices based on electronic properties. Additional discussions of inorganic aromatic compounds developed in this century, which give rise to new concepts like multifold aromaticity, are included. Three-dimensional aromaticity found in fullerenes and nanotubes, Möbius aromaticity present in some annulenes, and excited state aromaticity are explored as well. This volume explores the geometrical, electronic, magnetic, and thermodynamic characteristics of aromatic and antiaromatic compounds and their reactivity propTable of ContentsForeword xi Preface xiii List of Abbreviations xvii 1 Historical Overview 1 References 7 2 Simple Electron Counting Rules 11 2.1 Introduction 11 2.2 Hückel’s 4n +2 Rule 12 2.3 Baird’s 4n π-Electron Rule for the Lowest-Lying Triplet Excited State 13 2.4 Soncini and Fowler’s Rule 16 2.5 Möbius’ 4n π-Electron Rule 16 2.6 The Linking Number Rule 18 2.7 Platt’s Ring Perimeter Model 19 2.8 Clar’s π-Sextet Rule 20 2.8.1 Glidewell and Lloyd’s Rule 23 2.8.2 The Y-Rule 23 2.9 Hirsch’s 2(n +1)2 Rule 24 2.10 The 2n2 +2n+ 1 (S = n+ 1/2) Rule 26 2.11 Wade–Mingos’ 2n+ 2 Rule 26 2.11.1 Jemmis’ mno Rule 27 2.11.2 Equivalence between Hückel’s andWade–Mingos’ Rules 28 2.12 Other Rules 29 References 30 3 Aromaticity from Organic to Inorganic Compounds 35 3.1 Introduction 35 3.2 π-Aromatic Inorganic Species 36 3.3 Aromaticity in Main Group Metal Compounds 42 3.4 Aromaticity in Transition Metal Compounds 44 3.5 Conclusions 49 References 49 4 Stability and Reactivity in Aromatic Compounds 55 4.1 Introduction 55 4.2 Aromaticity and Thermodynamic Stability 56 4.3 Aromaticity and Kinetic Stability 61 4.3.1 Acenes 61 4.3.2 Pericyclic Reactions 64 4.3.2.1 Diels–Alder Cycloadditions 65 4.3.2.2 [2+2+2] Cycloadditions 67 4.3.2.3 [1,7]-Sigmatropic Migrations 68 4.3.2.4 Fullerene Additions 68 References 72 5 Descriptors of Aromaticity: Geometric Criteria 77 5.1 Introduction 77 5.2 Geometry-Based Estimation of the Molecular Energy 78 5.3 Bond Length Alternation as a Basis for Defining Aromaticity Indices 80 5.3.1 The Julg Aromaticity Index AJ 81 5.3.2 The Harmonic Oscillator Model of Aromaticity, HOMA (1972 and 1993) 82 5.4 Separation of HOMA into Two Components EN and GEO (1996) 85 5.5 Harmonic Oscillator Model of Electron Delocalization, HOMED (2007) 86 5.6 Harmonic Oscillator Model for Heterocycles with π Electron and/or n-Electron Delocalization: The HOMHED Index (2012) 87 5.7 Applications of the Bond Orders for Estimating Aromaticity 88 5.8 Bird’s Aromaticity Indices I5 and I6 (1985) 90 5.9 Pozharskii Criterion of Aromaticity, ΔN (1985) and Bond Alternation Coefficient, BAC (1995) 90 5.10 Applications 91 5.11 Impact of the Electric Field on Aromaticity 94 5.12 Stacking Interactions versus H-Bonding in Nucleobases 95 5.13 Showing the Interaction Path for Substituent Effects 96 5.14 Applications in the Field of Quasiaromatic Systems 100 5.15 Extension of HOMA to Noncyclic and Non-π-electron Systems 101 5.16 Conclusions 103 References 104 6 Descriptors of Aromaticity: Energetic Criteria 111 6.1 Introduction 111 6.2 Thermochemical Approaches 114 6.3 Energetic Approaches Based on Molecular Geometry 115 6.4 Theoretical Approaches 117 References 126 7 Descriptors of Aromaticity: Magnetic Criteria 131 7.1 Introduction 131 7.2 NMR Chemical Shifts 134 7.3 Nucleus Independent Chemical Shifts 135 7.4 Magnetically Induced Current Densities 138 7.5 Anisotropy of the Induced Current Density Tensor 140 References 141 8 Descriptors of Aromaticity: Electronic Criteria 145 8.1 Introduction 145 8.2 Density Functions 146 8.3 Measures of Electron Delocalization 150 8.3.1 The Electron Sharing Indices (ESI) 150 8.3.2 The Electron Localization Function (ELF) 152 8.4 Electronic Descriptors of Aromaticity 155 References 160 9 Heteroaromaticity 165 9.1 Introduction 165 9.2 Six-Membered Organic and Inorganic Heterocycles 168 9.3 Polycyclic Heteroaromatic Hydrocarbons 178 9.4 Five-Membered Organic Heterocycles 179 9.5 Aromaticity of Nucleic Bases 183 References 187 10 Möbius Aromaticity 193 10.1 Introduction 193 10.2 Metallacyclic Möbius Aromatic Species 197 10.3 Macrocyclic Möbius Aromaticity 199 References 204 11 𝛔-, 𝛑-, 𝛅-, and 𝛗-Aromaticity 207 11.1 Introduction 207 11.2 σ-Aromatic and σ-Antiaromatic Species 209 11.2.1 σ-Aromatic Species 209 11.2.2 σ-Antiaromatic Species 210 11.3 σ-, π-Doubly Aromatic, and σ-, π-Doubly Antiaromatic Species and Species with σ-, π-Conflicting Aromaticity 211 11.3.1 σ-, π-Doubly Aromatic Species 211 11.3.2 σ-, π-Doubly Antiaromatic Species 212 11.3.3 Species with σ-Antiaromaticity and π-Aromaticity 213 11.3.4 Species with σ-Aromaticity and π-Antiaromaticity 214 11.4 δ-Aromaticity 215 11.5 ϕ-Aromaticity 218 11.6 Conclusions 219 References 220 12 The Distortivity of 𝛑-Electrons 223 12.1 Introduction 223 12.2 The Kekulean Distortion 224 12.3 Frequencies of the Kekulé Vibrational Mode in Benzene 225 12.4 Changes in Aromaticity in the Kekulean Distortion 227 12.5 The Maximum Hardness and Minimum Polarizability Principles 228 12.6 The Distortive Nature of π-Electrons 229 12.7 Conclusions 236 References 236 13 Three-Dimensional Aromaticity 241 13.1 Introduction 241 13.2 Spherical Aromaticity 242 13.2.1 Aromaticity on the Surface of the Sphere 242 13.2.2 Aromaticity Inside the Sphere 247 13.2.2.1 Closo Boranes 248 13.2.2.2 Jellium Cluster Model 250 13.3 Octahedral Aromaticity 251 13.4 Cubic Aromaticity 253 13.5 Tetrahedral Aromaticity 255 13.6 Cylindrical Aromaticity 256 References 259 14 Excited State Aromaticity 265 14.1 Introduction 265 14.2 Theoretical and Experimental Studies of Excited State Aromaticity 266 14.2.1 Theoretical and Computational Studies 267 14.2.2 Experimental Studies 269 14.3 Influence of Aromaticity in the Excited State Properties 271 14.3.1 Molecular Dipole Moments 271 14.3.2 Singlet-Triplet Energy Gaps 272 14.3.3 Photoacidity 273 14.4 Influence of Aromaticity in the Excited State Reactivity 274 14.4.1 Photoisomerizations 275 14.4.2 Excited State Intramolecular Proton Transfer 276 14.4.3 Photochemical Formation of Ortho-Xylylenes 278 14.4.4 Photochemical Pericyclic Reactions 279 References 281 Index 285
£112.50
John Wiley & Sons Inc Green Techniques for Organic Synthesis and
Book SynopsisAn updated overview of the rapidly developing field of green techniques for organic synthesis and medicinal chemistry Green chemistry remains a high priority in modern organic synthesis and pharmaceutical R&D, with important environmental and economic implications. This book presents comprehensive coverage of green chemistry techniques for organic and medicinal chemistry applications, summarizing the available new technologies, analyzing each technique's features and green chemistry characteristics, and providing examples to demonstrate applications for green organic synthesis and medicinal chemistry. The extensively revised edition of Green Techniques for Organic Synthesis and Medicinal Chemistry includes 7 entirely new chapters on topics including green chemistry and innovation, green chemistry metrics, green chemistry and biological drugs, and the business case for green chemistry in the generic pharmaceutical industry.It is divided into 4 parts. The Table of ContentsList of Contributors xvii Foreword xxi Preface xxiii Part I General Topics in Green Chemistry 1 Green ChemistryMetrics 3Frank Roschangar and Juan Colberg 1.1 Business Case 3 1.2 Historical Context 3 1.3 Metrics, Awards, and Barriers 4 1.4 Metrics Unification Via Green Aspiration Level 9 1.5 Green Scorecard 12 1.6 Supply Chain 14 1.7 Outlook and Opportunities 15 References 17 Green Solvents 21Janet L. Scott and Helen F. Sneddon 2.1 Introduction 21 2.2 Solvent Selection Guides and Tools 23 2.3 Greener Molecular Solvents 24 2.4 Opportunities, Challenges, and Future Developments 34 References 34 Green Analytical Chemistry 43Paul Ferguson and Douglas Raynie 3.1 Introduction 43 3.2 Sample Preparation 47 3.3 Techniques and Methods 50 3.4 Process Analytical Technology 60 3.5 Biopharmaceutical Analysis 62 3.6 Conclusions 65 Acknowledgments 66 References 66 Green Engineering 71Christopher L. Kitchens and Lindsay Soh 4.1 Introduction: Green Engineering Misconceptions and Realizations 71 4.2 12 Principles of Green Engineering 72 4.3 Green Chemistry Metrics Applied to Engineering 73 4.4 Use of Green Solvents in the Chemical Industry 80 4.5 Presidential Green Chemistry Awards 86 4.6 Opportunities and Outlook 87 References 87 Greening of Consumer Cleaning Products 91David C. Long 5.1 History of Green Consumer Cleaning Products 91 5.2 Drivers for Greener Products 94 5.3 Development of Green Cleaning Criteria and Eco-Labeling 98 5.4 Development of Greener Ingredients for Cleaners 102 5.5 The Future of Green Cleaning 111 Acknowledgments 112 References 112 Innovation with Non-Covalent Derivatization 117John C.Warner and Emily Stoler 6.1 Introduction 117 6.2 NCD Overview 118 6.3 Pharmaceutical NCDs 121 6.4 Environmental and Green Chemistry Benefits 123 References 123 Part II Green Catalysts 131 Catalytic C-H Bond Cleavage for Heterocyclic Compounds 133Zhanxiang Liu and Yuhong Zhang 7.1 Introduction 133 7.2 Synthesis of Nitrogen Heterocycles 133 7.3 Synthesis of Oxygen-Containing Heterocycles 144 7.4 Synthesis of Sulfur-Containing Heterocycles 148 7.5 Medium-Sized Heterocyclic Compounds 150 7.6 Conclusion 152 References 152 Biocatalysis 161James Lalonde 8.1 Introduction 161 8.2 Enzymes for Biocatalysis 162 8.3 Advances in Enzyme Engineering and Directed Evolution 164 8.4 Biocatalytic Synthesis of Pharmaceuticals: Case Studies of Highly Efficient Pharmaceutical Syntheses 165 8.5 Summary and Future Outlook 178 References 180 Practical Asymmetric Organocatalysis 185Wen-Zhao Zhang, Samik Nanda, and Sanzhong Luo 9.1 Introduction 185 9.2 Aminocatalysis 185 9.3 Brønsted Acid Catalysis 191 9.4 Brønsted Base Catalysis 193 9.5 Hydrogen-Bonding Catalysis 197 9.6 Phase-Transfer Catalysis 202 9.7 Lewis Acid, Lewis Base, and N-Heterocyclic Carbene Catalysis 204 9.8 Large-Scale Reaction (>100-Gram Reaction) 207 9.9 Conclusion 209 References 209 Fluorous Catalysis 219L´aszl´o T. Mika and Istv´an T. Horv´ath 10.1 Introduction and the Principles of Fluorous Catalysis 219 10.2 Ligands for Fluorous Transition Metal Catalysts 224 10.3 Synthetic Application of Fluorous Catalysis 225 10.4 Fluorous Organocatalysis 256 10.5 Other Applications of Fluorous Catalysis 259 References 259 Solid-Supported Catalysis 269Sukanta Bhattacharyya and Basudeb Basu 11.1 Introduction 269 11.2 Immobilized Palladium Catalysts 270 11.3 Immobilized Rhodium Catalysts 276 11.4 Immobilized Ruthenium Catalysts 279 11.5 Other Immobilized Catalysts 284 11.6 Conclusions 286 References 287 Asymmetric Organocatalysis in Aqueous Media 291Kartick C. Bhowmick and Tanmoy Chanda 12.1 Introduction 291 12.2 Carbon-Carbon Bond-Formation Reactions 292 12.3 Reactions Other than C-C Bond Formation 313 12.4 Conclusion 314 References 314 Part III Green Synthetic Techniques 325 Solvent-Free Synthesis 327Kendra Leahy Denlinger and JamesMack 13.1 Introduction 327 13.2 Ball Milling 328 References 339 Ultrasonic Reactions 343Rodrigo Cella and H´elio A. Stefani 14.1 Introduction 343 14.2 How Does CavitationWork? 343 14.3 Aldol/Condensation Reactions 345 14.4 1,4-Addition 351 14.5 Heterocycles Synthesis 353 14.6 Coupling Reactions 356 14.7 Wittig Reaction 361 14.8 Diels-Alder Reaction 362 14.9 Miscellaneous 365 14.10 Conclusions 366 References 366 Photochemical Synthesis 373Stefano Protti,Maurizio Fagnoni, and Angelo Albini 15.1 Introduction 373 15.2 Synthesis and Rearrangement of Open-Chain Compounds 376 15.3 Synthesis of Three- and Four-Membered Rings 382 15.4 Synthesis of Five-, Six- (and Larger)-Membered Rings 391 15.5 Oxygenation and Oxidation 398 15.6 Conclusions 400 Acknowledgments 401 References 401 Pot Economy Synthesis 407Wenbin Yi, Xin Zeng, and Song Gao 16.1 Introduction 407 16.2 Multicomponent Reactions 407 16.3 One-Pot and Multi-Step Reactions 415 16.4 One-Pot Asymmetric Synthesis 424 16.5 Outlook 434 References 434 Microwave-Assisted Organic Synthesis: Overview of Recent Applications 441Nandini Sharma, Upendra K. Sharma, and Erik V. Van der Eycken 17.1 Introduction 441 17.2 C-H Functionalization 449 17.3 Insertion Reactions 452 17.4 Reduction 453 17.5 Synthesis of Peptides and Related Fine Chemicals 455 17.6 Newer Developments 459 17.7 Summary 461 References 461 Solid-Supported Synthesis 469Indrajeet J. Barve and Chung-Ming Sun Abbreviations 469 18.1 Introduction 471 18.2 Techniques of Solid-Phase Supported Synthesis 472 18.3 Solid-Phase Supported Heterocyclic Chemistry 476 18.4 Solid-Supported Synthesis of Natural Products 486 18.5 Solid-Supported Organometallic Chemistry 491 18.6 Solid-Phase Synthesis of Peptides 493 18.7 Solid-Phase Supported Stereoselective Synthesis 494 18.8 Interdisciplinary Solid-Supported Synthesis 499 References 505 Light Fluorous Synthesis 509Wei Zhang 19.1 Introduction 509 19.2 “Heavy” Versus “Light” Fluorous Chemistry 509 19.3 The Green Chemistry Aspects of Fluorous Synthesis 510 19.4 Fluorous Techniques for Discovery Chemistry 511 19.5 Conclusions 533 References 533 Part IV Green Techniques and Strategies in the Pharmaceutical Industry 539 Ionic Liquids in Pharmaceutical Industry 541Julia L. Shamshina, Paula Berton, HuiWang, Xiaosi Zhou, Gabriela Gurau, and Robin D. Rogers Abbreviations 541 20.1 Introduction 543 20.2 Finding the Right Role for ILs in the Pharmaceutical Industry 544 20.3 Conclusions and Prospects 567 References 568 Green Technologies and Approaches in theManufacture of Biologics 579Sa V. Ho and Kristi L. Budzinski 21.1 Introduction 579 21.2 Characteristics of Biologics 580 21.3 Manufacture of Therapeutic Biologics 581 21.4 Environmental Metrics Development and Impact Analysis 587 21.5 Some Future Directions 592 21.6 Conclusions 594 Acknowledgments 594 References 594 Benchmarking Green Chemistry Adoption by “Big Pharma”and Generics Manufacturers 601Vesela R. Veleva and BerkeleyW. Cue 22.1 Introduction 601 22.2 Literature Review 602 22.3 Pharmaceutical Industry Overview and Green Chemistry Drivers 604 22.4 Benchmarking Industry Adoption of Green Chemistry 607 22.5 Results and Discussion 610 22.6 Conclusion 616 References 616 Green Process Chemistry in the Pharmaceutical Industry: Case Studies Update 621Joseph M. Fortunak, Ji Zhang, Frederick E. Nytko III, and Tiffany N. Ellison 23.1 Introduction 621 23.2 Pharmaceutical Patents Driving Innovation 622 23.3 A Caution About Drug Manufacturing Costs 623 23.4 Process Evolution by Multiple Route Discovery Efforts—Dolutegravir 624 23.5 The Impact of Competition on Process Evolution—Tenofovir Disoproxil Fumarate 628 23.6 Simeprevir (Olysio/Sovriad) and Analogues: Chiral Phase-Transfer Catalyst-Promoted Optical Alpha-Amino Acid Synthesis: A Metal-free Process 633 23.7 Vaniprevir (MK 7009), Simeprevir (TMC435), and Danoprevir: Ring-Closing Metathesis (RCM) for Macrocyclic Lactam Synthesis: Now a Commercial Reality 635 23.8 Daclatasvir (BMS-790052, Daklinza), and Ledipasvir (GS-5885): Palladium Catalyzed Cross-Coupling for Greening a Process 638 23.9 Sitagliptin (Januvia) and Ponatinib (Iclusig): Greening the Process by Telescoping Multiple Steps Together 639 23.10 Febuxostat (Uloric): Greening the Process via Metal Catalyzed C-H Activation: A Prospect 641 23.11 Conclusions 644 References 644 Greener Pharmaceutical Science Through Collaboration: The ACS GCI Pharmaceutical Roundtable 649Julie B. Manley andMichael E. Kopach 24.1 Introduction 649 24.2 Establishing Pre-Competitive Collaborations 650 24.3 Informing and Influencing the Research Agenda 654 24.4 Developing Tools 661 24.5 Educating Leaders 666 24.6 Collaborating Globally 668 24.7 Future Opportunities 669 24.8 Success Factors 671 References 673 Index 675
£143.06
John Wiley & Sons Inc Organic Reactions Volume 95
Book SynopsisThe 95th volume in this series for organic chemists in industry presents critical discussions of widely used organic reactions or particular phases of a reaction. The material is treated from a preparative viewpoint, with emphasis on limitations, interfering influences, effects of structure and the selection of experimental techniques. The work includes tables that contain all possible examples of the reaction under consideration. Detailed procedures illustrate the significant modifications of each method.Table of Contents1. The Julia–Kocienski Olefination 1Paul R. Blakemore, Selena Milicevic Sephton, and Engelbert Ciganek 2. Asymmetric Synthesis of β-Lactams by the Staudinger Reaction 423Aitor Landa, Antonia Mielgo, Mikel Oiarbide, and Claudio Palomo Cumulative Chapter Titles by Volume 595 Author Index, Volumes 1–95 613 Chapter and Topic Index, Volumes 1–95 619
£200.70
John Wiley & Sons Inc PlantBased Natural Products
Book SynopsisThe book deals with novel applications of plant derived natural agents and their derivatives in the food, textile dyeing, medicinal, and environmental areas. Plant based natural products and their derivatives have strong influence on our everyday lives. They are needed for many everyday applications ranging from food, medicine, agriculture, textiles, and healthcare. This new book presents significant research advances about the use of plant-based natural products, mainly dyes and pigments, bioactive compounds and other plant extracts in the textile coloration, food, medicine, bioremediation and environmental applications. The topics of the ten informative chapters in Plant-Based Natural Products include the following: potential resurgence of natural dyes in applied fields; natural colorants from indigoid rich plants; phytochemical and pharmacological aspects of Butea monosperma plant; irradiation as novel pretreatment methods to improve wash fastness propTable of Contents Preface xiii 1 Potential Resurgence of Natural Dyes in Applied Fields 1Shahid Adeel, Sana Rafi, Mahwish Salman, Fazal-Ur-Rehman and Shazia Abrar 1.1 Introduction 1 1.2 History 3 1.3 Advantages of Natural Dyes 4 1.4 Classification 5 1.5 Methods of Extraction and Dyeing 10 1.6 Potential Application of Natural Dyes 12 1.7 Conclusion 20 Acknowledgment 20 References 20 2 Natural Dyes from Indigoid-Rich Plants: An Overview 27Mohd Yusuf and Shahid-ul-Islam 2.1 Introduction to Natural Dyes 27 2.2 Indigoid Dyes: An Overview 29 2.4 Safety Aspects and Sustainability 43 2.5 Conclusion and Future Outlook 43 References 44 3 Phytochemical and Pharmacological Aspects of Butea monosperma L. 47Shahid-ul-Islam, Mohd Yusuf and Faqeer Mohammad 3.1 Introduction 48 3.2 Phytochemical Aspects 49 3.3 Sterols 52 3.4 Imides 52 3.5 Terpenoids 54 3.6 Miscellaneous Compounds 55 3.7 Biological Activities 55 3.8 Conclusion 61 References 61 4 Radiation Pretreatment: A Potential Novel Technology to Improve Fastness Properties of Plant-Derived Natural Dyes 65Shahid Adeel, Shumaila Kiran, Sana Rafi, Tayyaba Ayesha, Fazal-Ur-Rehman, Tahsin Gulzar and M.Zuber 4.1 Introduction 66 4.2 Chemistry of Fabrics 69 4.3 Mordants and their Classification 73 4.4 Radiation and its Role in Dyeing 76 4.5 Applications of Mordants 78 4.6 Conclusion 81 Acknowledgments 81 References 82 5 Natural Colorant from Lawsonia inermis Leaves: Reflectance Spectroscopy-Induced Optimal Conditions of Extraction and Dyeing 89Mohd Yusuf and Faqeer Mohammad 5.1 Introduction 89 5.2 Materials and Methods 91 5.3 Results and Discussion 93 5.4 Conclusion 98 Acknowledgement 100 References 100 6 Plant Food By-products and their Application in Food Industry 103Kaiser Younis, Ovais Shafiq Qadri, Khalid Bashir and Shahid-ul-Islam 6.1 Introduction 103 6.2 Plant Origin Food By-products 105 6.3 Effects on the Quality Parameters of Food Products Incorporated with Plant By-products 112 6.4 Conclusion 121 References 122 7 Effect of Drumstick Leaves (Moringa oleifera) Incorporation on Quality of Khakhra 129TaranjitKaur Maghu, Alka Sharma and Kaiser Younis 7.1 Introduction 130 7.2 Materials and Methods 131 7.3 Results and Discussions 134 Conclusion 142 Acknowledgments 142 References 142 8 Curcumin and Its Derivatives – Isolation, Synthesis, and Applications 145Ovas Ahmad Dar, Manzoor Ahmad Malik, Shahid-ul-Islam, Parveez Gull and Athar Adil Hashmi 8.1 Introduction 145 8.2 Isolation 147 8.3 Metal Complexes as Derivatives of Curcumin 147 8.4 Applications of Curcumin and its Derivatives 156 8.5 Conclusions and Future Perspective 166 Abbreviations 167 References 168 9 Investigating the Functional Properties of Pineapple Pomace Powder and Its Incorporation in Buffalo Meat Products 175Kaiser Younis and Saghir Ahmad 9.1 Introduction 175 9.2 Materials and Methods 176 9.3 Results and Discussion 180 Conclusion 189 Acknowledgment 190 References 190 10 Green Adsorbents from Plant Sources for the Removal of Arsenic: An Emerging Wastewater Treatment Technology 193Sharf Ilahi Siddiqui, Saif Ali Chaudhry and Shahid-ul-Islam 10.1 Introduction 194 10.2 Arsenic Toxicity 195 10.3 Detoxification and Remediation of Arsenic 196 10.4 Adsorption as an Emerging Technology 197 10.5 Mechanism Followed by Green Adsorbent 205 10.6 Water Constraints Effect on Green Adsorbent 207 10.7 Regeneration of Green Adsorbent 208 10.8 Advantages, Shortcomings, and Recent Advances 210 10.9 Conclusion and Future Prospects 211 Acknowledgment 211 References 211
£152.06
John Wiley & Sons Inc Spiro Compounds
Book SynopsisSPIRO COMPOUNDS A comprehensive treatment of the latest research in, and applications of, spiro compounds Spiro Compounds: Synthesis and Applications combines discussions of the latest advances in spiro compound research with the most cutting-edge, real-world applications of that knowledge. This book provides in-depth coverage of the history, significance, properties, synthetic methods, and applications of spiro compounds. As interest in spiro compounds grows due to their unique conformational features and their structural implications on biological systems, Spiro Compounds delivers fulsome treatments of advances in spiro compound synthesis (including stereoselective synthesis) methodologies. With a special focus on the mechanisms of the reactions that lead to the synthesis of spiro compounds, chapters in the book cover topics such as: The history, significance, and unique properties of spiro compounds The most important methodolTable of ContentsList of Contributors xi Preface xiii 1 Spiro Compounds: A Brief History 1Marta Meazza 1.1 Notes on IUPAC Rules for Spiro Compounds 6 References 7 2 Selected Applications of Spirocycles in Medicinal Chemistry 9Matthias Baud 2.1 Introduction 9 2.2 General Features 15 2.3 Property Optimization in Bioactive Compounds 17 2.4 Four-Membered Rings: Synthesis, Applications, and New Design Principles 19 2.5 Further Examples 26 2.6 Conclusions 28 References 29 3 Recent Advances in the Asymmetric Synthesis of Spiro Compounds Through Cycloadditions 35Alberto Vega-Peñaloza, Suva Paria, Luca Dell’Amico, and Xavier Companyó 3.1 Introduction 35 3.2 Organometallic Methodologies 36 3.2.1 Organometallic [3+2] Cycloaddition Strategies to Construct Spiro Compounds 36 3.2.2 Organometallic [4+2] Cycloaddition Strategies to Construct Spiro Compounds 42 3.2.3 Organometallic Miscellaneous Strategies to Construct Spiro Compounds 44 3.3 Organocatalytic Methodologies 48 3.3.1 Organocatalytic [3+2] Cycloaddition Strategies to Construct Spiro Compounds 48 3.3.2 Organocatalytic [4+2] Cycloaddition Strategies to Construct Spiro Compounds 52 3.3.3 Organocatalytic [4+3] and [2+2] Cycloaddition and Switchable Strategies to Construct Spirocompounds 55 3.3.4 Organocatalytic Miscellaneous Strategies to Construct Spiro Compounds 60 References 62 4 Design and Synthesis of Spirocycles via Olefin Metathesis 65Sambasivarao Kotha, Vikas R Aswar and Yellaiah Tangella 4.1 Introduction 65 4.2 Formation of Aza-spirocycles 84 4.3 Formation of Oxa-spirocycles 87 4.4 Miscellaneous Examples 97 References 98 5 Spirooxindoles: Synthesis via Organocatalytic Processes 103Peng-Wei Xu, Xiao-Yuan Cui, Jin-Sheng Yu, and Jian Zhou 5.1 Introduction 103 5.2 Enamine and Iminium Catalysis 105 5.3 Chiral Nucleophilic Catalysis with Tertiary Phosphines or Amines 114 5.4 Chiral N-Heterocyclic Carbene Catalysis 120 5.5 Chiral Tertiary Amine-H-Bond Donor Bifunctional Catalysis 127 5.6 Chiral Hydrogen-Bonding Catalysis 142 5.7 Chiral Phosphoric Acid Catalysis 144 5.8 Chiral Phase-Transfer Catalysis 149 5.9 Chiral Organoiodine Catalysis 151 5.10 Conclusion 153 References 153 6 Spirooxindole Synthesis by Organometallic Processes 161Albert Moyano 6.1 Introduction 161 6.2 Direct Construction of the Spirooxindole Unit by Cyclization Methodologies 161 6.2.1 Intramolecular Heck Reaction and Related Cyclizations 161 6.2.2 Alkylation–Cyclization of 3-Substituted Oxindoles 167 6.2.3 Cyclization of 3-Substituted Indoles 170 6.3 Two-component Annulation/Cycloaddition Methodologies 171 6.3.1 Cyclopropyl Spirooxindoles by [2+1] Cycloaddition Reactions 171 6.3.2 [2+2] Cycloaddition Reactions 173 6.3.3 [3+2] Annulation/Cycloaddition Reactions 175 6.3.4 [3+3] Cycloaddition Reactions 188 6.3.5 [4+1] Cycloaddition Reactions 189 6.3.6 [4+2] Cycloaddition/Annulation Reactions 190 6.3.7 [5+2] Cycloaddition Reactions 195 6.4 Miscellaneous Methods 195 6.4.1 Darzens Reaction of Isatins 195 6.4.2 Cyclization of 3,3-Disubstituted Oxindoles 198 6.4.3 Three-component Reactions 198 6.5 Conclusions 200 Acknowledgements 200 References 200 7 Enantioselective Synthesis of Spiro Heterocycles 205Michal Urban and Jan Veselý 7.1 Introduction 205 7.2 Enantioselective Synthesis of Spiro Heterocycle with One Nitrogen Atom 206 7.2.1 Enantioselective Formation of Spiropyrrolidines 206 7.2.1.1 Organometallic Approaches 206 7.2.1.2 Organocatalytic Approaches 208 7.2.1.3 Cooperative-catalytic Approaches 209 7.2.2 Enantioselective Formation of Spirocycles Containing Indoline and Indolenine Ring 210 7.2.2.1 Organometallic Approaches 210 7.2.2.2 Organocatalytic Approaches 211 7.2.3 Enantioselective Formation of Spiropiperidines 214 7.2.3.1 Organometallic Approaches 214 7.2.3.2 Organocatalytic Approaches 216 7.3 Enantioselective Formation of Spirocycles Containing Heterocycle with One Oxygen Atom 218 7.3.1 Enantioselective Formation of Spirocycles Containing Dihydrofuranone and Tetrahydrofuran Ring 218 7.3.1.1 Organometallic Approaches 218 7.3.1.2 Organocatalytic Approaches 221 7.3.2 Enantioselective Formation of Spirocycles Containing Benzofuranone and Benzodihydrofuran Ring 224 7.3.2.1 Organometallic Approaches 224 7.3.2.2 Organocatalytic Approaches 227 7.3.2.3 Cooperative-catalytic Approaches 233 7.3.3 Enantioselective Formation of Spirocycles Containing Dihydrocoumarin, Dihydro- and Tetrahydropyran Ring 234 7.3.3.1 Organometallic Approaches 234 7.3.3.2 Organocatalytic Approaches 236 7.4 Enantioselective Formation of Sulfur-containing Spirocycles 240 7.5 Enantioselective Formation of Spirocycles Containing Heterocycle with More Than One Heteroatom 244 7.5.1 Enantioselective Formation of Spirocycles Containing Pyrazolone Ring 244 7.5.1.1 Organometallic Approaches 244 7.5.1.2 Organocatalytic Approaches 246 7.5.1.3 Cooperative-catalytic Approaches 255 7.5.2 Chapter 7.5.2 – Enantioselective Formation of Spirocycles Containing Barbituric Acid and Hydantoin 256 7.5.3 Chapter 7.5.3 – Enantioselective Formation of Spirocycles Containing Azlactones 259 7.5.3.1 Organometallic Approaches 259 7.5.3.2 Organocatalytic Approaches 259 7.5.3.3 Cooperative-catalytic Approaches 259 7.5.4 Chapter 7.5.4 – Enantioselective Formation of Spirocycles Containing Rhodanines and Sultams 262 7.5.4.1 Organometallic Approaches 262 7.5.4.2 Organocatalytic Approaches 264 7.5.5 Chapter 7.5.5 – Enantioselective Formation of Spiroketals (Spiroacetals) 266 7.5.5.1 Organometallic Approaches 267 7.5.5.2 Organocatalytic Approaches 268 7.5.5.3 Cooperative-catalytic Approaches 269 7.6 Enantioselective Formation of Other Spiro Heterocyclic Systems 270 7.6.1 Organometallic Approaches 270 7.6.1.1 Organocatalytic Approaches 272 7.7 Enantioselective Formation of Bispirocycles 273 7.8 Conclusion 274 Acknowledgements 275 References 275 8 Enantioselective Synthesis of all Carbon Spiro Compounds 283Ramon Rios 8.1 Enantioselective Synthesis of All-Carbon Spiro Compounds Based on Alkylation Methods 285 8.2 Enantioselective Synthesis of All-Carbon Spirocycles by Metal-catalyzed Methods 286 8.3 Enantioselective Synthesis of All-Carbon Spirocycles by Cycloaddition Strategies 294 8.4 Enantioselective Synthesis of All-Carbon Spirocycles by Radical Strategies 300 8.5 Enantioselective Synthesis of All-Carbon Spirocycles by Cascade Reactions 301 8.6 Enantioselective Synthesis of All-Carbon Spirocycles by Rearrangement Strategies 307 8.7 Conclusions 310 References 310 9 Transition-Metal-Catalyzed Dearomative Spiroannulation Reactions 313Lu Bai, Jingjing Liu and Xinjun Luan 9.1 Introduction: Discovery of Aromatic Compounds 313 9.2 Development of Dearomatization Reactions 313 9.3 Development of Dearomative Spiroannulation Reactions 314 9.4 Dearomative Spiroannulations of Phenols 314 9.4.1 Dearomative Spiroannulation Without Oxidants 315 9.4.1.1 Dearomative Alkylation of Phenols 315 9.4.1.2 Dearomative Arylation of Phenols 319 9.4.2 C–H Bond Activation/Dearomative Spiroannulation Reactions 325 9.5 Dearomative Spiroannulation of Indoles 332 9.5.1 Intramolecular Dearomative Allylic Alkylation 332 9.5.2 Intramolecular Dearomative Arylation 334 9.5.3 Intermolecular Dearomative Spiroannulation of Indoles 338 9.6 Dearomative Spiroannulation of Aromatic Heterocyclic Compounds 342 9.6.1 Dearomative Spiroannulation of Pyrroles 342 9.6.2 Dearomative Spiroannulation of Furans 344 9.6.3 Dearomative Spiroannulation of Thiophenes 346 9.7 Dearomative of Other Aromatic Compounds 349 9.8 Conclusion 352 References 352 10 Carbocyclic Spiro Compounds Occupying Higher Dimensions: Benzoannelated [5.5.5.5]Fenestranes and Beyond 357Hak-Fun Chow and Dietmar Kuck 10.1 Introduction 357 10.2 Selected Synthesis Strategies 362 10.2.1 The Access to Benzoannelated Fenestranes 365 10.2.2 Derivatives of [5.5.5.6]-Fenestranones and Fenestrindane 371 10.2.3 Fenestrindanes as a Core Embedded in a Closed π-Electron Periphery 378 10.2.4 Three Spiranes Merged in a Centropolycyclic Framework: Centrohexaindane and Its Derivatives 384 10.3 Conclusions 392 Acknowledgements 394 References 394 11 The Synthesis of Natural Products Containing Spirocycles 401Ramon Rios 11.1 Porco’s Synthesis of (+)-Calafianin 401 11.2 Hayashi’s Total Synthesis of Pseurotin A 405 11.3 Trost’s Synthesis of (−)-Ushikulide A 408 11.4 Castle’s and Herzon’s Syntheses of (−)Acutumine 412 11.4.1 Castle’s Synthesis of (−)-acutamine 413 11.4.2 Herzon’s Synthesis of (−)-Acutumine 417 11.5 Overman’s and Carreira’s Synthesis of Spirotryprostatin B 421 11.5.1 Overman’s Synthesis of Spirotryprostatin B 421 11.5.2 Carreira’s Synthesis of (−)-Spirotryprostatin B 423 11.6 Conclusion 427 References 427 Index 429
£161.06
John Wiley & Sons Inc Organic Reaction Mechanisms 2019
Book SynopsisOrganic Reaction Mechanisms 2019, the 55th annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2019. The following classes of organic reaction mechanisms are comprehensively reviewed: Reaction of Aldehydes and Ketones and their DerivativesReactions of Carboxylic, Phosphoric, and Sulfonic Acids and their DerivativesOxidation and ReductionCarbenes and NitrenesNucleophilic Aromatic SubstitutionElectrophilic Aromatic SubstitutionCarbocationsNucleophilic Aliphatic SubstitutionCarbanions and Electrophilic Aliphatic SubstitutionElimination ReactionsPolar Addition ReactionsCycloaddition ReactionsMolecular RearrangementsRadicals An experienced team of authors compile these reviews every year, so that the reader can rely on a continuing quality of selection and presentation.Table of Contents1 Reactions of Aldehydes and Ketones and Their Derivatives 1B. A. Murray 2 Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and Their Derivatives 43C. T. Bedford 3 Oxidation and Reduction 65R. N. Mehrotra 4 Carbenes and Nitrenes 141E. Gras and S. Chassaing 5a Nucleophilic Aromatic Substitution 179M. R. Crampton 5b Electrophilic Aromatic Substitution 213G.W.Weaver 6 Carbocations 257V. M. Moreira 7 Nucleophilic Aliphatic Substitution 2019 287J. G. Moloney and M. G. Moloney 8 Carbanions and Electrophilic Aliphatic Substitution 321M. L. Birsa 9 Elimination Reactions 333M. L. Birsa 10 Addition Reactions: Polar Addition 345P. Kocovsky 11 Addition Reactions: Cycloaddition 473N. Dennis 12 Molecular Rearrangements 519J. M. Coxon 13 Ligand-Promoted Catalysed Reactions 555I. Bosque and J. C. Gonzalez-Gomez 14 Radical Reactions 597S. R. Hussaini Author Index 633 Subject Index 683
£477.00
John Wiley & Sons Inc Asymmetric Synthesis of Natural Products
Book SynopsisTable of ContentsPreface List of Abbreviations Chapter 1 Introduction Chapter 2 Chirality, Topology, and Asymmetric Synthesis Chapter 3 Asymmetric Synthesis Chapter 4 Sugars Chapter 5 Amino Acids, Peptides, and Proteins Chapter 6 Nucleosides, Nucleotides, and Nucleic Acids Chapter7 Phenylpropanoids Chapter 8 Polyketides Chapter 9 Isoprenoids or Terpenes Chapter 10 Alkaloids References Index
£63.60
John Wiley & Sons Inc Polysaccharides
Book SynopsisThis book provides the whole spectrum of polysaccharides from basic concepts to commercial market applications. Chapters cover various types of sources, classification, properties, characterization, processing, rheology and fabrication of polysaccharide-based materials and their composites and gels. The applications of polysaccharides include in cosmetics, food science, drug delivery, biomedicine, biofuel production, marine, packaging, chromatography and environmental remediation. It also reviews the fabrication of inorganic and carbon nanomaterials from polysaccharides. The book incorporates industrial applications and will fill the gap between the exploration works in the laboratory and viable applications in related ventures.Table of ContentsPreface xxiii 1 Natural Polysaccharides From Aloe vera L. Gel (Aloe barbadensis Miller): Processing Techniques and Analytical Methods 1Silvana Teresa Lacerda Jales, Raquel de Melo Barbosa, Girliane Regina da Silva, Patricia Severino and Tulio Flávio Accioly de Lima Moura 1.1 Introduction 2 1.1.1 Gel Composition from A. vera 3 1.2 Applications of A. vera Mucilaginous Gel or Fractions 5 1.3 Aloe vera Gel Processing 5 1.3.1 Obtaining Polysaccharide Fraction or Acemannan 8 1.4 Analytical Methods Applied 9 1.4.1 Total Carbohydrates, Oligosaccharides, Acemannan and Free Sugars 9 1.4.2 Analytical Techniques 12 1.4.2.1 Chromatography Analysis 12 1.4.2.2 Infrared Spectroscopy (IR) 13 1.4.2.3 Nuclear Magnetic Resonance Spectroscopy 14 1.4.2.4 Mass Spectrometry 15 1.4.2.5 Ultraviolet–Visible Spectroscopy 16 1.4.2.6 Comprehensive Microarray Polymer Profiling 16 1.5 Conclusion 17 References 17 2 Cell Wall Polysaccharides 23Ata Ullah, Lutufur Rahman, Muhammad Bilal Yazdani, Muhammad Irfan, Waheed S. Khan and Asma Rehman 2.1 Introduction to Cell Wall 23 2.2 Plant Cell Wall Polysaccharides 24 2.2.1 Cellulose 24 2.2.2 Hemicellulose 25 2.2.2.1 Xyloglucan 25 2.2.2.2 Xylans 25 2.2.2.3 Mannans 26 2.2.3 Callose 26 2.2.4 Pectic Polysaccharides 26 2.2.4.1 Homogalacturonan (HG) 27 2.2.4.2 Arabinan 27 2.3 Algal Cell Wall Polysaccharides 28 2.3.1 Alginates 28 2.3.2 Sulfated Galactans 28 2.3.3 Fucoidans 30 2.4 Fungal Cell Wall Polysaccharides 30 2.4.1 Glucan 31 2.4.2 Chitin and Chitosan 31 2.5 Bacterial Cell Wall Polysaccharides 32 2.5.1 Peptidoglycan 32 2.5.2 Lipopolysaccharides 33 References 33 3 Marine Polysaccharides: Properties and Applications 37Tonmoy Ghosh, Rabinder Singh, Asha Arumugam Nesamma and Pannaga Pavan Jutur 3.1 Introduction 37 3.2 Polysaccharide Origins 38 3.3 Properties 38 3.3.1 Cellulose 38 3.3.2 Chitosan 40 3.3.3 Alginate 41 3.3.4 Carrageenan 41 3.3.5 Agar 41 3.3.6 Porphyran 42 3.3.7 Fucoidan 42 3.3.8 Ulvan 42 3.3.9 Exopolysaccharides From Microalgae 43 3.4 Applications of Polysaccharides 44 3.4.1 Biomedical Applications 44 3.4.1.1 Cellulose 44 3.4.1.2 Chitosan 44 3.4.1.3 Alginate 45 3.4.2 Food Applications 45 3.4.2.1 Cellulose 45 3.4.2.2 Chitosan 46 3.4.2.3 Alginates 46 3.4.2.4 Carrageenan 47 3.4.2.5 Agar 47 3.4.3 Pharmaceutical and Nutraceutical Applications 47 3.4.3.1 Cellulose 47 3.4.3.2 Chitosan 47 3.4.3.3 Alginate 48 3.4.3.4 Carrageenan 48 3.4.3.5 Porphyran 49 3.4.3.6 Fucoidan 49 3.4.4 Agriculture 50 3.5 Conclusions 50 References 51 4 Seaweed Polysaccharides: Structure, Extraction and Applications 61Oya Irmak Şahin 4.1 Introduction 61 4.1.1 Agar 62 4.1.2 Carrageenan 63 4.1.3 Alginate (Alginic Acid, Algin) 65 4.1.4 Fucoidan 67 4.1.5 Laminaran 68 4.1.6 Ulvan 69 4.2 Conclusion 70 References 70 5 Agars: Properties and Applications 75Sudhakar Padmesh and Aditi Singh 5.1 History and Origin of Agar 75 5.1.1 Agarophytes Used in Agar Manufacturing 76 5.2 Physical Properties of Agar Producing Seaweeds 76 5.3 Agar Manufacturing 78 5.3.1 Types of Agar Manufacturing 78 5.3.1.1 Freeze–Thaw Method 78 5.3.1.2 Syneresis Method 78 5.4 Structure of Agar 79 5.5 Heterogeneity of Agar 80 5.6 Physico-Chemical Characteristics of Agar 80 5.7 Chemical Characteristics of Agar 82 5.8 Factors Influencing the Characteristics of Agar 83 5.8.1 Techniques to Analyze the Fine Chemical Structure of Agar 85 5.8.2 Synergies and Antagonisms of Agar Gels 86 5.9 Uses of Agar in Various Sectors 87 5.9.1 Applications of Agar in Food Industry 88 5.9.2 Application of Agar in Harvesting Insects and Worms 89 5.9.3 Vegetable Tissue Culture Formulations 90 5.9.4 Culture Media for Microbes 91 5.9.5 Industrial Applications of Agar 91 5.10 Conclusion and Discussion 91 References 92 6 Biopolysaccharides: Properties and Applications 95Sinem Tunçer 6.1 Structure and Classification of Biopolysaccharides 95 6.1.1 Structure 95 6.1.2 Classification 97 6.1.3 Structural Characterization Techniques 98 6.2 Uses and Applications of Biopolysaccharides 99 6.2.1 Functional Fibers 100 6.2.2 Biomedicine 101 6.2.2.1 Tissue Engineering 102 6.2.2.2 Wound Healing 107 6.2.2.3 Drug Loading and Delivery 110 6.2.2.4 Therapeutics 114 6.2.3 Cosmetics 115 6.2.4 Foods and Food Ingredients 116 6.2.5 Biofuels 119 6.2.6 Wastewater Treatment 120 6.2.7 Textiles 121 6.3 Conclusion 122 References 123 7 Chitosan Derivatives: Properties and Applications 135Gincy Marina Mathew, Sarah Bill Ulaeto, Reshmy R., Rajeev Kumar Sukumaran, Parameswaran Binod, Ashok Pandey and Raveendran Sindhu 7.1 Introduction 135 7.2 Properties of Chitosan Derivatives 142 7.2.1 Physiochemical Properties 142 7.2.2 Functional Properties 143 7.2.3 Biological Properties of Chitosan 144 7.3 Applications of Chitosan Derivatives 145 7.3.1 Anticancer Agents 145 7.3.2 Bone Tissue Material Formation 147 7.3.3 Wound Healing, Tissue Regeneration and Antimicrobial Resistance 148 7.3.4 Drug Delivery 149 7.3.5 Chromatographic Separations 150 7.3.6 Waste Management 150 7.3.7 Food Industry 151 7.3.8 In Cosmetics 152 7.3.9 In Paint as Antifouling Coatings 152 7.4 Conclusions 152 Acknowledgement 153 References 153 8 Green Seaweed Polysaccharides Inventory of Nador Lagoon in North East Morocco 163El Asri Ouahid, Ramdani Mohamed and Fadlaoui Soufiane 8.1 Introduction 163 8.2 Nador Lagoon: Situation and Characteristics 164 8.3 Seaweed 165 8.4 Polysaccharides in Seaweed 166 8.5 Algae Polysaccharides in Nador Lagoon’s Seaweed 167 8.5.1 C. prolifera 167 8.5.1.1 Sulfated Galactans 168 8.5.2 U. rigida & E. intestinalis 168 8.5.2.1 Ulvan 169 8.5.3 C. adhaerens, C. bursa, C. tomentosum 170 8.5.3.1 Sulfated Arabinans 170 8.5.3.2 Sulfated Arabinogalactans 170 8.5.3.3 Mannans 171 8.6 Conclusion 172 References 172 9 Salep Glucomannan: Properties and Applications 177Abdullah Kurt 9.1 Introduction 177 9.2 Production 179 9.3 Composition and Physicochemical Structure 181 9.4 Rheological Properties 183 9.5 Purification and Deacetylation 188 9.6 Food Applications 191 9.6.1 Beverage 191 9.6.2 Ice Cream and Emulsion Stabilizing 192 9.6.3 Edible Film/Coating 194 9.6.4 Gelation 195 9.7 Health Benefits 196 9.8 Conclusions and Future Trends 197 References 198 10 Exudate Tree Gums: Properties and Applications 205Aruna Jyothi Kora 10.1 Introduction 205 10.1.1 Gum Arabic 206 10.1.2 Gum Karaya 208 10.1.3 Gum Kondagogu 209 10.1.4 Gum Ghatti 209 10.1.5 Gum Tragacanth 210 10.1.6 Gum Olibanum 211 10.2 Nanobiotechnology Applications 211 10.3 Minor Tree Gums 214 10.4 Conclusions 214 Acknowledgment 217 References 218 11 Cellulose and its Derivatives: Properties and Applications 221Rafael de Avila Delucis, Pedro Henrique Gonzalez de Cademartori, André Ricardo Fajardo and Sandro Campos Amico 11.1 Introduction 221 11.2 Main Raw Materials 222 11.3 Composition and Chemical Structure of Lignocellulosic Materials 224 11.4 Cellulose: Chemical Backbone and Crystalline Formats 225 11.5 Cellulose Extraction 228 11.5.1 Mechanical Methods 228 11.5.2 Chemical Methods 231 11.6 Cellulose Products and its Derivatives 232 11.7 Main Applications 236 11.8 Conclusion 241 References 242 12 Starch and its Derivatives: Properties and Applications 253Bhanita Goswami and Debajyoti Mahanta 12.1 Introduction 253 12.2 Physicochemical and Functional Properties of Starch 254 12.2.1 Size, Morphology and Crystallinity of Starch Granules 255 12.2.2 Physical Properties due to Associated Lipids, Proteins and Phosphorus With Starch Granules 257 12.2.3 Solubility and Swelling Capacity of Starch 257 12.2.4 Gelatinization and Retrogradation of Starch 258 12.2.5 Birefringence and Glass Transition Temperature of Starch 259 12.2.6 Rheological and Thermal Properties of Starch 260 12.2.7 Transmittance and Opacity of Starch 260 12.2.8 Melt Processability of Starch 261 12.3 Modification of Starch 261 12.3.1 Physical Modification of Starch 262 12.3.2 Chemical Modification of Starch 263 12.3.3 Dual Modification of Starch 265 12.3.4 Enzymatic Modification of Starch 265 12.3.5 Genetic Modification of Starch 265 12.4 Application of Starch and its Derivatives 266 12.4.1 In Food Industry 266 12.4.2 In Paper Industry 266 12.4.3 Starch as Binders 267 12.4.4 In Detergent Products 267 12.4.5 As Biodegradable Thermoplastic Materials or Bioplastics 267 12.4.6 In Pharmaceutical and Cosmetic Industries 268 12.4.7 As Industrial Raw Materials 269 12.4.8 As Adsorbents for Environmental Applications 269 12.4.9 As Food Packaging Materials 269 12.4.10 In Drug Delivery 270 12.4.11 As Antimicrobial Films and Coatings 270 12.4.12 In Advanced Functional Materials 271 12.5 Conclusion 273 References 274 13 Crystallization of Polysaccharides 283Mohsen Khodadadi Yazdi, Farzad Seidi, Yongcan Jin, Payam Zarrintaj, Huining Xiao, Amin Esmaeili, Sajjad Habibzadeh and Mohammad Reza Saeb 13.1 Introduction 283 13.2 Principles of Crystallization of Polysaccharides 285 13.3 Techniques for Crystallinity Measurement 287 13.4 Crystallization Behavior of Polysaccharides 287 13.4.1 Cellulose 287 13.4.2 Chitosan and Chitin 290 13.4.3 Starch 291 13.5 Polymer/Polysaccharide Crystalline Nanocomposites 293 13.6 Conclusion 293 References 294 14 Polysaccharides as Novel Materials for Tissue Engineering Applications 301Nandini A. Pattanashetti, Anand I. Torvi, Arun K. Shettar, Pramod B. Gai and Mahadevappa Y. Kariduraganavar 14.1 Introduction 301 14.2 Types of Scaffolds for Tissue Engineering 303 14.3 Biomaterials for Tissue Engineering 304 14.4 Polysaccharide-Based Scaffolds for Tissue Engineering 305 14.4.1 Alginate-Based Scaffolds 306 14.4.2 Chitosan-Based Scaffolds 307 14.4.3 Cellulose-Based Scaffolds 309 14.4.4 Dextran and Pullulan-Based Scaffolds 310 14.4.5 Starch-Based Scaffolds 311 14.4.6 Xanthan-Based Scaffolds 312 14.4.7 Glycosaminoglycans-Based Scaffolds 313 14.5 Current Challenges and Future Perspectives 316 Acknowledgements 317 References 317 15 Structure and Solubility of Polysaccharides 325Vickramjeet Singh, Shikha Indoria, K.J. Jisha and Ramesh L. Gardas 15.1 Introduction 325 15.2 Polysaccharide Structure and Solubility in Water 326 15.3 Solubility and Molecular Weight 329 15.4 Solubility and Branching 330 15.5 Polysaccharide Solutions 332 15.6 Conclusions 334 Acknowledgments 334 References 334 16 Polysaccharides: An Efficient Tool for Fabrication of Carbon Nanomaterials 337Yuliya Dzyazko and Vladimir Ogenko 16.1 Introduction 337 16.2 Aerogels 338 16.2.1 Plant and Bacterial Cellulose 339 16.2.2 Carbon Derived From Nanocrystalline Cellulose of Plant Origin 344 16.2.3 Carbon Aerogels Produced From Bacterial Cellulose 348 16.2.4 Chitosan and Sodium Alginate for Preparation of Carbon Aerogels 350 16.3 Graphene-Like Materials and Nanotubes Produced From Polysaccharides 352 16.4 Biocarbon Quantum Dots 355 16.5 Membranes Containing Carbon Nanoparticles Derived From Cellulose 356 16.6 Conclusions 358 References 358 17 Rheology and Structural Properties of Polysaccharides 367Andreea Irina Barzic 17.1 Introduction 367 17.2 General Structural Features of Polysaccharides 368 17.3 Main Types of Polysaccharides and Their Structural Properties 370 17.4 Rheological Behavior of Polysaccharides 374 17.4.1 Semi-Diluted and Concentrated Solutions of Polysaccharides 374 17.4.2 Gels of Polysaccharides 375 17.4.3 Polysaccharide Liquid Crystals 377 17.5 Conclusions 379 References 379 18 Gums-Based Bionanostructures for Medical Applications 385Hira Munir, Muhammad Bilal, Muhammad Imran Khan and Hafiz M.N. Iqbal 18.1 Plants and Their Bioactive Compounds 386 18.2 Natural Gums—Physicochemical Features 386 18.3 Sources of Natural Gums 387 18.3.1 Exudate Gums 387 18.3.2 Mucilages 387 18.3.3 Seaweed Polysaccharides 388 18.3.4 Microbial Polysaccharides 388 18.3.5 Animal Polysaccharide 388 18.3.6 Other Sources of Polysaccharide Gums 388 18.4 Classification of Gums 388 18.4.1 According to the Charge 388 18.4.2 According to the Source 389 18.4.3 According to Shape 389 18.4.4 According to Monomeric Units in Chemical Structure 389 18.4.5 Semi-Synthetic Gums 390 18.5 Composition of Natural Gums 390 18.6 Extraction and Purification of Natural Gums 390 18.7 Modification and Hydrolysis of Natural Gums 390 18.8 Medical Applications of Gums-Based Bio-Nanostructures 390 18.8.1 Conductive Adhesive Properties and Pharmaceutical Applications 391 18.8.2 Application in Imaging and Cell Studies 393 18.8.3 Application in Sutures 393 18.8.4 Biomaterials for Implantation 394 18.9 Conclusions 395 References 395 19 Alginates: Properties and Applications 399Sapna Raghav, Pallavi Jain and Dinesh Kumar 19.1 Introduction 399 19.2 Properties of Sodium Alginate (Na-Alg) 400 19.2.1 Thickening Property of Alginates 401 19.2.2 Gelling Property of Alginates 401 19.2.3 Film-Forming Property 402 19.2.4 Lipophilicity 402 19.2.5 Solubility 402 19.2.6 pH Sensitivity 402 19.3 Chemical Properties 402 19.4 Applications 403 19.4.1 Bone Tissue Engineering 404 19.4.2 Pharmaceutical Applications 405 19.4.2.1 Small Chemical Drug Delivery 405 19.4.2.2 Protein Delivery 406 19.4.3 Wound Dressing 406 19.4.4 Vaccine Delivery 408 19.4.5 Water Treatment Application 410 19.4.6 Alginate for Anion Removal 410 19.5 Conclusions and Prospects 414 Acknowledgments 414 Abbreviations 414 References 414 20 Marine Polysaccharides: Properties and Applications 423Olugbenga Samuel Michael, Charles Oluwaseun Adetunji, Ayodele Eugene Ayeni, Muhammad Akram, Inamuddin, Juliana Bunmi Adetunji, Mathew Olaniyan and Musa Abidemi Muhibi 20.1 Introduction 424 20.2 Marine Bacteria That Produce Polysaccharides 425 20.3 Marine Fungi That Produce Polysaccharide 431 20.4 Production, Extraction and Purification of Polysaccharides 431 20.4.1 Solid State Fermentation 432 20.4.2 Submerged Fermentation 432 20.4.3 Extraction and Purification of Polysaccharides 432 20.5 Characterization via Molecular, Biochemical and Cultural Characterization of Marine Polysaccharides 433 20.6 Conclusion and Future Recommendation to Knowledge 434 References 434 21 Polysaccharides: Promising Constituent for the Preparation of Nanomaterials 441Rafeeya Shams, Quratul Eain Hyder Rizvi, Aamir Hussain Dar, Ishrat Majid, Shafat Ahmad Khan and Anurag Singh 21.1 Introduction 441 21.1.1 Classification and Types of Nanomaterials 442 21.2 Preparation of Polysaccharide-Dependent Nanomaterials 445 21.2.1 Electrospinning 445 21.2.2 Dip Coating, Film Casting, and Physical Mixing 446 21.2.3 Layer by Layer Assembly 447 21.2.4 Ionotropic Gelation, Colloidal Assembly and Coprecipitation 447 21.2.5 In Situ NP Preparation 447 21.2.6 Ionotropic Gelation 448 21.3 Biocompatibility of Carbon-Based Nanomaterials 451 21.4 Conclusions and Summary 452 References 452 22 Anticancer Potential of Polysaccharides 459Ali Raza, Javed Iqbal, Muhammad Usman Munir, Anila Asif and Arsalan Ahmed 22.1 Introduction 459 22.2 Mode of Action 460 22.2.1 Cell-Cycle Arrest 460 22.2.2 Receptor 460 22.2.3 Immunomodulatory Effect 461 22.2.4 Chemotherapy Enhancement 461 22.2.5 Mitochondrial Membrane Inhibition 461 22.2.6 Free Radicals Capture 462 22.3 Polysaccharides in Cancer Treatment 462 22.3.1 Lung Cancer 463 22.3.2 Blood Cancer 464 22.3.3 Liver Cancer 465 22.3.4 Gastric and Colon Cancer 465 22.3.5 Bladder and Kidney Cancer 466 22.3.6 Breast Cancer 466 22.3.7 Cervical Cancer 467 22.4 Polysaccharides in Conventional Therapies 468 22.4.1 Chemotherapy 468 22.4.2 Radiotherapy 469 22.4.3 Surgery 469 22.4.4 Phototherapy 469 22.4.5 Drug Delivery 469 22.4.6 Bioimaging 470 22.4.7 Food Supplement 470 22.5 Concluding Remarks and Future Trends 471 References 471 23 Polysaccharide-Based Membrane for Packaging Applications 477Saumya Pandey 23.1 Introduction 477 23.2 Polysaccharides as Biomaterials for Biodegradable Packaging 478 23.2.1 Polysaccharides Extracted From Animals 481 23.2.1.1 Chitin and Chitosan 481 23.2.2 Polysaccharides Extracted From Plants 481 23.2.2.1 Cellulose 481 23.2.2.2 Pectin 482 23.2.2.3 Starch 483 23.2.2.4 Galactomannans 484 23.2.3 Polysaccharides Extracted From Algae 484 23.2.3.1 Carrageenan 484 23.2.3.2 Alginate 484 23.2.4 Polysaccharides Synthesized by Microorganisms 485 23.2.4.1 Pullulan 485 23.2.4.2 Gellan Gum 485 23.2.4.3 Xanthan Gum 486 23.2.4.4 FucoPol 486 23.3 Properties of Polysaccharide-Based Packaging Film or Coating 486 23.3.1 Barrier Properties of Film or Coatings 486 23.3.2 Mechanical Properties of the Film 488 23.4 Polysaccharides-Based Nanocomposites Packaging 489 23.5 Polysaccharides-Based Films and Coatings in Food Packaging Applications 490 23.5.1 Food Preservation and Self-Life Extension 490 23.5.2 Antimicrobial Coating 490 23.5.3 Delaying of Post-Harvest Ripening 491 23.5.4 Restoring Color, Aroma and Nutritional Value 491 23.5.5 Antioxidant Properties 491 23.6 Conclusion and Prospects 492 References 493 24 Applications of Polysaccharides in Cancer Treatment 501Nivedita Pujari S., Joy Hoskeri H., Anand I. Torvi and Arun K. Shettar 24.1 Introduction 501 24.2 Types of Polysaccharides Used in Cancer Treatment 502 24.2.1 Animal Polysaccharides 502 24.2.2 Vegetal Polysaccharides 503 24.2.3 Microorganism and Fungi Polysaccharides 503 24.3 Mechanism of Polysaccharides as Anticancer Agent 504 24.3.1 Actions of Polysaccharides as Immunological Functioning 504 24.3.2 Role of Polysaccharides in Cell Signaling 505 24.3.3 Effect of Polysaccharides in Apoptosis and Cell Cycle Arrest 506 24.3.4 Antitumor Effect of Polysaccharides 506 24.4 Usage of Polysaccharides in Preclinical and Clinical Models of Cancer 507 24.4.1 In-Vitro Cell Line Model 507 24.4.2 Polysaccharides as Antitumor/Anticancer in Animal Model Study 508 24.4.3 Clinical Trials of Polysaccharides in Cancer Treatment 508 24.5 Conclusion and Future Perspectives 510 References 510 25 Application of Chitosan-Based Catalysts for Heterocycles Synthesis and Other Reactions 517Yadavalli Venkata Durga Nageswar, Nelson L.C. Domingues, Ramesh Katla and Rakhi Katla 25.1 Introduction 517 25.2 Recent Research Reports 518 25.2.1 Furans 518 25.2.2 Pyrazoles 518 25.2.3 Imidazoles 519 25.2.4 Oxazoles 520 25.2.5 Thiazoles 521 25.2.6 Triazoles 522 25.2.7 Tetrazoles 523 25.2.8 Pyridines 524 25.2.9 Quinolines 524 25.2.10 Pyrazines 525 25.2.11 Pyrimidines 525 25.2.12 Quinazolines 527 25.2.13 Phthalazines 527 25.2.14 Perimidines 527 25.2.15 Pyrans 528 25.2.16 Coumarins 530 25.2.17 Chromenes 530 25.2.18 Other Reactions 531 25.2.18.1 Oxidations 531 25.2.18.2 Reductions 533 25.2.18.3 Coupling/Condensation Reactions 533 25.2.18.4 Isomerization 537 25.2.18.5 Ring Opening 538 25.3 Conclusion 538 References 539 26 Preparation and Applications of Polysaccharide-Based Composites 543Sadaf Ahmad, Bushra Anees Palvasha, Bakar bin Khatab Abbasi, Muhammad Shahid Nazir, Majid Niaz Akhtar, Zaman Tahir and Mohd Azmuddin Abdullah 26.1 Introduction 544 26.2 Types 544 26.2.1 Cellulose 544 26.2.2 Starch 545 26.2.3 Glycogen 545 26.2.4 Chitin 545 26.2.5 Pectin 546 26.3 Importance 546 26.4 Fabrication and Applications of Polysaccharide-Inorganic-Based Composites 547 26.4.1 Cellulose–Inorganic Materials 547 26.4.2 Starch–Inorganic Materials 553 26.4.3 Pectin–Inorganic Materials 557 26.4.4 Chitin and Chitosan–Inorganic Materials 559 26.4.5 Polysaccharides–Metal Organic Frameworks 561 26.5 Recent Applications 564 26.6 Conclusion 565 References 566 27 Polysaccharide-Based Liquid Crystals 573Sumaira Saleem, Gulzar Muhammad, Muhammad Mudassir Iqbal, Muhammad Ajaz Hussain, Muhammad Arshad Raza, Zahid Shafiq and Haseeba Razzaq 27.1 Introduction 573 27.2 Polysaccharides-Based Liquid Crystals 575 27.2.1 Cellulose-Based Liquid Crystals 575 27.2.2 Liquid Crystals From Cellulose Derivatives 578 27.2.3 Amylose-Based Liquid Crystals 579 27.2.4 Dextrin-Based Liquid Crystals 582 27.2.5 Chitin-Based Liquid Crystals 584 27.2.6 Schizophyllan-Based Liquid Crystals 585 27.3 Conclusion 586 References 586 28 Patents on Polysaccharide Applications 591Nadhratun Naiim Mobarak, Sharifah Nabihah Syed Jaafar and Mohamad Azuwa Mohamed 28.1 Introduction 591 28.2 Polysaccharides in Medical Application 595 28.3 Polysaccharides in Cosmetic Application 597 28.4 Polysaccharides in Battery Components 600 28.5 Polysaccharides in Paper Manufacture 601 28.6 Conclusion 601 References 602 29 Applications of Polysaccharides in Controlled Release Drug Delivery System 607Muhammad Harris Shoaib, Muhammad Sikandar, Farrukh Rafiq Ahmed, Fatima Ramzan Ali, Faaiza Qazi, Rabia Ismail Yousuf, Asma Irshad, Sabahat Jabeen and Kamran Ahmed 29.1 Introduction 607 29.2 Polysaccharides From Plant Sources and Their Derivatives 608 29.2.1 Cellulose 608 29.2.2 Cellulose Derivatives 609 29.2.2.1 Cellulose Ethers 609 29.2.2.2 Cellulose Esters 612 29.2.3 Hemicellulose 613 29.2.3.1 Mannans 614 29.2.4 Starch 617 29.2.5 Pectin 618 29.2.6 Lignin 619 29.2.7 Inulin 620 29.3 Gums 620 29.3.1 Exudate Gums 620 29.3.1.1 Gum Arabic (Gum Acacia) 620 29.3.1.2 Gum Tragacanth 621 29.3.1.3 Gum Karaya 621 29.3.2 Mucilage Gums 622 29.3.2.1 Okra Gum 622 29.3.2.2 Khaya Gum 622 29.3.2.3 Hakea Gum 622 29.3.2.4 Cassia tora Gum 623 29.3.2.5 Albizia Gum 623 29.3.2.6 Prunus cerasoides Gum 623 29.3.2.7 Tamarind Gum 623 29.3.2.8 Cissus populnea Gum 624 29.4 Polysaccharides From Algal Sources 624 29.4.1 Alginates 624 29.4.2 Galactans 626 29.4.3 Carrageenan 626 29.4.4 Agar 627 29.4.5 Agarose 628 29.5 Polysaccharides From Fungal Sources 629 29.5.1 Scleroglucan 629 29.5.2 Beta-Glucan 629 29.5.3 Pullulan 630 29.6 Polysaccharides From Animals Sources and Their Derivatives 631 29.6.1 Chitin 631 29.6.2 Chitosan 632 29.6.3 Hyaluronic Acid 633 29.6.4 Glycogen 633 29.6.5 Chondroitin Sulfate 633 29.6.6 Dermatan Sulfate 634 29.6.7 Gelatin 634 29.7 Polysaccharides From Microorganisms 635 29.7.1 Curdlan 635 29.7.2 Xanthan Gum 636 29.7.3 Gellan Gum 637 References 637 30 Applications of Polysaccharides in Nutrition and Medicine 657Nivedita Pujari S., Arun K. Shettar and Joy Hoskeri H. 30.1 Introduction 657 30.2 Sources of Polysaccharides 658 30.2.1 Polysaccharides in Dietary Fibers 658 30.2.2 Polysaccharides in Plants 659 30.2.3 Polysaccharides in Algae and Lichens 659 30.2.4 Polysaccharides in Fungi 660 30.2.5 Polysaccharides From Bacteria 661 30.2.6 Polysaccharides From Other Sources 662 30.3 Role of Polysaccharides in Nutrition 662 30.3.1 Polysaccharides in Food 662 30.3.2 Polysaccharides as Energy Sources 663 30.3.3 Health Impact of Polysaccharides 664 30.3.4 Nutritional Aspect of Polysaccharides 664 30.4 Biomedical Applications of Polysaccharides 665 30.4.1 Polysaccharides as Antimicrobial and Antiviral 665 30.4.2 Polysaccharides as Antitumor/Anticancer 666 30.4.3 Polysaccharides as Anti-Obesity and Anti-Hypercholesterolemic Agents 667 30.4.4 Polysaccharides as Antidiabetic Agents 669 30.4.5 Polysaccharides as Immune Modulator Agent 670 30.4.6 Polysaccharides as Anti-Inflammatory Agent 671 30.4.7 Polysaccharides as Neuro-Protective Agent 672 30.4.8 Polysaccharides as a Source of Antioxidant 672 30.4.9 Polysaccharides in Wound Healing and Wound Dressing 673 30.5 Conclusion 674 References 674 31 Synthetic Polysaccharide-Based Vaccines: Progress and Achievements 683Rafig Gurbanov 31.1 A Brief History of Vaccination 683 31.2 The Leverage of Synthetic Polysaccharide-Based Vaccines Over Natural Polysaccharide-Based Vaccines 684 31.3 The Principles of Synthetic Polysaccharide-Based Vaccines 686 31.3.1 Tumor Vaccines 689 31.3.2 Leishmaniasis Vaccines 690 31.3.3 Human Immunodeficiency Virus Vaccines 690 31.3.4 Bacterial Vaccines 691 31.4 The Opportunities and Prospects of Synthetic Polysaccharide-Based Vaccine Technologies 692 References 694 32 Polysaccharides Derived From Natural Sources: A Panacea to Health and Nutritional Challenges 701Charles Oluwaseun Adetunji, Muhammad Akram, Olugbenga Samuel Michael, Khuram Shahzad, Ayodele Eugene Ayeni, Sidra Hasan, Juliana Bunmi Adetunji, Syed Muhammad Hasan, Inamuddin, Mathew Olaniyan and Musa Abidemi Muhibi 32.1 Introduction 702 32.2 Different Types of Polysaccharides Derived From Different Natural Sources 703 32.2.1 Polysaccharides Derived From Plants and Their Applications 704 32.2.2 Animal Derived Polysaccharides and Their Applications 705 32.2.2.1 Chitosan and Chitin 705 32.2.2.2 Heparin and Heparin Sulfates 706 32.2.2.3 Hyaluronic Acid 707 32.2.3 Microorganisms Derived Polysaccharides and Their Applications 707 32.2.3.1 Alginate 707 32.2.3.2 Dextran 708 32.2.3.3 Fucoidans 708 32.2.3.4 Spirulina 708 32.2.4 Homoglycans 709 32.2.4.1 Starch and Hetastarch 709 32.2.4.2 Cellulose 709 32.2.4.3 Inulin 710 32.2.4.4 Chitin and Chitosan 710 32.2.4.5 Glycogen 712 32.2.4.6 Heteroglycans and Other Polysaccharides 712 32.2.4.7 Glycosaminoglycans Significance 715 32.2.4.8 Chondroitin Sulfates 715 32.2.4.9 Hyaluronic Acid 715 32.2.4.10 Alginic Acid 715 32.2.4.11 Mucopolysaccharidoses 717 32.3 Production, Extraction and Purification of Polysaccharides 718 32.3.1 Solid State Fermentation 719 32.3.2 Submerged Fermentation 719 32.3.3 Extraction and Purification Process of Polysaccharides 720 32.4 Specific Examples of Polysaccharides and Their Various Applications in Nutrition and Medicine 720 32.4.1 Schizophyllan 720 32.4.1.1 Antitumor Activity of Schizophyllan 721 32.4.1.2 Anti-Inflammatory Activity of Schizophyllan 721 32.4.1.3 Immunomodulatory Activity of Schizophyllan 721 32.4.1.4 Prebiotic Potential of Schizophyllan 722 32.4.2 Pleuran and Others Polysaccharides From Pleurotus spp. 722 32.4.2.1 Specific Nutritional and Beneficial Functions of Pleurotus Polysaccharides 722 32.4.3 Scleroglucan 723 32.4.3.1 Applications for Nutritional and Medicinal Purposes Derived From Scleroglucan 723 32.4.4 Curdlan 724 32.4.5 Other Essential Polysaccharides With Medical Significance 725 32.5 Conclusion and Recommendation to Knowledge 725 References 725 Index 739
£206.06
John Wiley & Sons Inc The Systematic Identification of Organic
Book SynopsisThe Systematic Identification of Organic Compounds A comprehensive introduction to the identification of unknown organic compounds Identifying unknown compounds is one of the most important parts of the study of chemistry. From basic characteristics such as melting and/or boiling point to more complex data generated through cutting-edge techniques, the range of possible methods for identifying unknown organic compounds is substantial. The utility of a research reference which compiles known techniques and characteristics of possible compounds is clear. The Systematic Identification of Organic Compounds provides such a reference, designed to teach a hands-on approach in the chemistry lab. It takes readers step-by-step through the process of identifying an unknown compound and elucidating its structure from infrared, nuclear magnetic resonance, and mass spectra in addition to solubility characteristics, melting point, boiling point, and classificatioTable of ContentsPreface ix About the Companion Website xi Chapter 1 Introduction 1 1.1 Systematic Identification of Organic Compounds: The Need for Organic Qualitative Analysis 1 1.2 Suggestions to Students and Instructors 3 Chapter 2 Laboratory Safety 7 2.1 Working Safely in the Laboratory 7 2.2 Training 10 2.3 Personal Protection Equipment 10 2.4 Safety Data Sheets 11 2.5 Storage of Chemicals 12 2.6 Disposal of Chemicals 13 2.7 Safely Using Equipment in the Laboratory 13 Chapter 3 Identification of Unknowns 15 3.1 Discussion of Report Form 15 3.2 Preliminary Examination 22 3.3 Physical Properties 22 3.4 Molecular Weight Determination 22 3.5 Molecular Formula Determination 23 3.6 Solubility Tests 23 3.7 Infrared, Nuclear Magnetic Resonance, and Mass Spectra Analyses 24 3.8 Classification Tests 24 3.9 Preparation of a Satisfactory Derivative 25 3.10 Mixtures 26 3.11 Report Forms 26 Chapter 4 Preliminary Examination, Physical Properties, and Elemental Analysis 31 4.1 Preliminary Examination 32 4.2 Determination of Physical Properties 34 4.3 Optical Rotation 53 4.4 Recrystallization 58 4.5 Qualitative Elemental Analysis 61 4.6 Quantitative Elemental Analysis 69 Chapter 5 Classification of Organic Compounds by Solubility 75 5.1 Solubility in Water, Aqueous Acids and Bases, and Ether 76 5.2 Solubility in Organic Solvents 95 Chapter 6 Separation of Mixtures 99 6.1 Preliminary Examinations of Mixtures 100 6.2 Distillation and Sublimation 101 6.3 Extractions: Separations Based Upon 6.4 Chromatography 119 Chapter 7 Nuclear Magnetic Resonance Spectrometry 145 7.1 Theory of Nuclear Magnetic Resonance 145 7.2 Preparation of the Sample 149 7.3 Proton Spectra 151 7.4 13C Spectra 165 7.5 DEPT 179 7.6 COSY 188 7.7 HSQC 190 Chapter 8 Infrared Spectrometry 227 8.1 Theory of Infrared Spectrometry 227 8.2 Preparation of the Sample 230 8.3 Functional Group Identification 234 Chapter 9 Mass Spectrometry 269 9.1 Theory of Mass Spectrometry 269 9.2 Cleavage Reactions 271 Chapter 10 Chemical Tests for Functional Groups 293 10.1 Acid Anhydrides 296 10.2 Acyl Halides 306 10.3 Alcohols 307 10.4 Aldehydes 323 10.5 Amides 332 10.6 Amines and Amine Salts 334 10.7 Amino Acids 349 10.8 Carbohydrates 351 10.9 Carboxylic Acids 359 10.10 Esters 360 10.11 Ethers 361 10.12 Halides 365 10.13 Hydrocarbons--Alkanes 371 10.14 Hydrocarbons--Alkenes 371 10.15 Hydrocarbons--Alkynes 378 10.16 Hydrocarbons--Aromatic 379 10.17 Ketones 384 10.18 Nitriles 386 10.19 Nitro Compounds 386 10.20 Phenols 389 10.21 Sulfonamides, Sulfonic Acids, Sulfonyl Chlorides 393 Chapter 11 The Preparation of Derivatives 397 11.1 Carboxylic Acids, Acid Anhydrides, Acid Halides 397 11.2 Alcohols 409 11.3 Aldehydes And Ketones 414 11.4 Amides 420 11.5 Amines 424 11.6 Amino Acids 432 11.7 Carbohydrates 437 11.8 Esters 440 11.9 Ethers--Aliphatic 450 11.10 Ethers--Aromatic 451 11.11 Halides--Alkyl 454 11.12 Halides--Aromatic 457 11.13 Hydrocarbons--Aromatic 460 11.14 Nitriles 462 11.15 Nitro Compounds 467 11.16 Phenols 468 11.17 Sulfonic Acids, Sulfonyl Chlorides, Sulfonamides 472 Chapter 12 Chemical Literature 479 12.1 Handbooks 480 12.2 Compendia 480 12.3 Spectral Collections 481 12.4 Journals 482 12.5 Abstracts and Indexes 483 12.6 Monographs 486 Appendix I Handy Tables for the Organic Laboratory 487 APPENDIX II Table of Derivatives 493 Appendix III Equipment and Chemicals for the Laboratory 677 Index 685
£98.96
John Wiley & Sons Inc The Systematic Identification of Organic
Book SynopsisThe Student Solutions Manual to accompany The Systematic Identification of Organic Compounds, 9th Edition is an essential resource for any student using the parent text in class. Providing complete solutions to all practice problems provided in the textbook, this book allows you to assess your understanding of difficult material and clarify complex topics. Fully aligned with the text, this book details structures, formulas, mechanisms, and more to help you pinpoint areas of difficulty and focus your study time for more efficient learning.Table of ContentsPreface vii Chapter 4 Preliminary Examination, Physical Properties, and Elemental Analysis 1 Chapter 5 Classification of Organic Compounds by Solubility 5 Chapter 6 Separation of Mixtures 13 Chapter 7 Nuclear Magnetic Resonance Spectrometry 23 Chapter 8 Infrared Spectrometry 45 Chapter 9 Mass Spectrometry 51 Chapter 10 Chemical Tests for Functional Groups 55 Chapter 11 The Preparation of Derivatives 73 Chapter 13 Structural Problems 117 Problem Set 1 117 Problem Set 2 120 Problem Set 3 144 Problem Set 4 166 Problem Set 5 169 Problem Set 6 172 Problem Set 7 178 Problem Set 8 183 Problem Set 9 188 Problem Set 10 192 Problem Set 11 197 Problem Set 12 203 Problem Set 13 207 Problem Set 14 211 Problem Set 15 218 Problem Set 16 224 Problem Set 17 228 Problem Set 18 232 Problem Set 19 237 Problem Set 20 242
£43.22
John Wiley & Sons Inc Chiral Separations and Stereochemical Elucidation
Book SynopsisAn expert resource for chemists using stereochemical analysis methods In Chiral Separations and Stereochemical Elucidation: Fundamentals, Methods, and Applications, a team of distinguished researchers delivers a robust and authoritative discussion of the theoretical fundamentals of chiral separation, the most commonly used chiral selectors, and stereochemical elucidation methods. The book offers expert discussions of a variety of chiral separation methods by gas chromatography (GC), supercritical fluid chromatography (SFC), capillary electrophoresis (CE), and liquid chromatography (LC). The authors also describe several methods for stereochemical elucidation, including X-ray crystallography, nuclear magnetic resonance spectroscopy, and chiroptical methods. The explored material is ideal for practicing chemists seeking a resource to help them guide method development and optimization or to explain quality control-complements during target compound production. RTable of ContentsList of Contributors xv Preface xix Part I Fundamentals of Chiral Separation 1 1 Chiral Separation by LC 3 Juliana Cristina Barreiro and Quezia Bezerra Cass 1.1 Introduction 3 1.2 Workflow for LC Chiral Method Development 7 1.3 New Column Technologies 9 1.4 Selected Examples of Fast Separation 12 1.5 Chiral 2D- LC 14 1.5.1 LC–LC and mLC–LC 14 1.5.2 LC × LC and sLC × LC 17 1.6 Future and Perspectives 19 References 20 2 Chiral Separation by GC 27 Oliver Trapp 2.1 Introduction 27 2.2 Chiral Recognition in Gas Chromatography 29 2.2.1 Chiral Recognition by Hydrogen Bonding 31 2.2.2 Chiral Recognition Using Chiral Metal Complexes 31 2.2.3 Chiral Recognition by Host–Guest Interactions 31 2.3 Preparation of Fused- Silica Capillaries for GC with CSPs 33 2.4 Application of CSPs in Chiral Gas Chromatography 34 2.4.1 CSPs with Diamide Selectors 34 2.4.1.1 Chirasil- Val 34 2.4.2 CSPs with CD Selectors 35 2.4.2.1 Heptakis(2,3,6- tri- O- Methyl)- β- Cyclodextrin (Permethyl- β- Cyclodextrin) 38 2.4.2.2 Heptakis(2,3,6- tri- O- Methyl)- β- Cyclodextrin Immobilized to Hydrido Dimethyl Polysiloxane (Chirasil- β- Dex) 39 2.4.2.3 Heptakis(2,6- di- O- Methyl- 3- O- Pentyl)- β- Cyclodextrin 43 2.4.2.4 Hexakis- (2,3,6-tri- O- Pentyl)- α- Cyclodextrin 47 2.4.2.5 Heptakis(2,3,6- tri- O- Pentyl)- β- Cyclodextrin 48 2.4.2.6 Hexakis- (3- O- Acetyl- 2,6- di- O- Pentyl)- α- Cyclodextrin 51 2.4.2.7 Heptakis(3- O- Acetyl- 2,6- di- O- Pentyl)- β- Cyclodextrin 51 2.4.2.8 Octakis(3- O- Butyryl- 2,6- di- O- Pentyl)- γ- Cyclodextrin 53 2.4.2.9 Hexakis/Heptakis/Octakis(2,6- di- O- Alkyl- 3- O- Trifluoroacetyl)- α/β/γ- Cyclodextrins 57 2.4.2.10 Heptakis(2,3- di- O- Acetyl- 6- O-tert- Butyldimethylsilyl)- β- Cyclodextrin (DIAC- 6- TBDMS- β- CD) 58 2.4.2.11 Heptakis(2,3- di- O- Methyl- 6- O-tert- Butyldimethylsilyl)- β- Cyclodextrin (DIME- 6- TBDMS- β- CD) 58 2.4.3 Cyclofructans 62 2.4.4 CSPs with Metal Complexes 65 2.5 Conclusion 69 References 69 3 Chiral Separation by Supercritical Fluid Chromatography 85 Emmanuelle Lipka 3.1 Introduction 85 3.2 Characteristics and Properties of Supercritical Fluids 87 3.3 Development of a Chiral SFC Method 89 3.3.1 Chiral Stationary Phases 89 3.3.2 Mobile Phases 91 3.3.2.1 Mobile Phase: Type of Co- solvent Used 93 3.3.2.2 Mobile Phase: Percentage of Co- solvent Used 94 3.3.2.3 Mobile Phase: Use of Additives 94 3.4 Operating Parameters 94 3.4.1 Effect of the Flow Rate 95 3.4.2 Effect of the Outlet Pressure (Back- pressure) 95 3.4.2.1 Effect of Pressure When the Mobile Phase is a Gas- Like Fluid 96 3.4.2.2 Effect of Pressure When the Mobile Phase is a Liquid- Like Fluid 97 3.4.3 Effect of Temperature 97 3.4.3.1 Effect of Temperature When the Mobile Phase is a Gas- Like Fluid 98 3.4.3.2 Effect of Temperature When the Mobile Phase is a Liquid- Like Fluid 98 3.5 Detection 99 3.6 Scale- Up to Preparative Separation 99 3.7 Conclusion 100 References 101 4 Chiral Separation by Capillary Electrophoresis and Capillary Electrophoresis–Mass Spectrometry: Fundamentals, Recent Developments, and Applications 103 Charles Clark, Govert W. Somsen, and Isabelle Kohler 4.1 Introduction 103 4.2 Principles of Chiral CE 105 4.2.1 Electrophoretic Mobility 105 4.2.2 CE Separation Efficiency 106 4.2.3 Chiral Resolution in CE 107 4.2.4 Chiral Micellar Electrokinetic Chromatography and Capillary Electrochromatography 109 4.3 Short History of Chiral CE Modes 111 4.3.1 Chiral CE 111 4.3.2 Chiral MEKC and Chiral CEC 111 4.4 State of the Art and Recent Developments 112 4.4.1 Common Chiral Selectors 112 4.4.2 Ionic Liquids as Chiral Selectors 117 4.4.3 Nanoparticles as Chiral Selector Carriers 117 4.4.4 Microfluidic Chiral CE 118 4.5 Applications of Chiral CE 119 4.5.1 Pharmaceutical Analysis 119 4.5.2 Food Analysis 120 4.5.3 Environmental Analysis 121 4.5.4 Bioanalysis 123 4.5.5 Forensic Analysis 126 4.6 Chiral CE- MS: Strategies and Challenges 126 4.6.1 Hyphenation Approaches 129 4.6.1.1 Sheath–Liquid and Sheathless CE- MS Interfacing 129 4.6.1.2 Partial- Filling Techniques 130 4.6.1.3 Counter- Migration Techniques 131 4.6.2 Chiral MEKC- MS 132 4.6.3 Chiral CEC- MS 133 4.7 Conclusions and Perspectives 135 References 135 5 Chiral Separations at Semi and Preparative Scale 143 Larry Miller 5.1 Introduction 143 5.2 Selection of Operating Conditions 145 5.3 Batch HPLC Purification 146 5.3.1 Analytical Method Development for Preparative Separations 146 5.3.2 Batch HPLC Examples 148 5.3.2.1 Batch HPLC Example 1 148 5.3.2.2 Batch HPLC Example 2 149 5.4 Steady- State Recycle Introduction 151 5.4.1 SSR Example 1 153 5.5 Simulated Moving Bed Chromatography – Introduction 154 5.5.1 SMB Examples for R&D and Separation of Compound 2 156 5.5.2 Development of a Manufacturing SMB Process (Compound 1) 158 5.5.3 Cost for SMB Processes 160 5.6 Introduction to Supercritical Fluid Chromatography 161 5.6.1 Analytical Method Development for Scale- up to Preparative SFC 162 5.6.2 Preparative SFC Example 1 163 5.6.3 Preparative SFC Example 2 163 5.7 Options for Increasing Purification Productivity 165 5.7.1 Closed- Loop Recycling 165 5.7.2 Stacked Injections 166 5.7.3 Choosing the Best Synthetic Intermediate for Separation 167 5.7.3.1 Choosing Synthetic Step for Separation – HPLC/SMB Example 168 5.7.3.2 Choosing Synthetic Step for Separation – SFC Example 169 5.7.4 Use of Non- Commercialized CSP 170 5.7.5 Immobilized CSP for Preparative Resolution 173 5.7.5.1 Processing of Low Solubility Racemate 173 5.7.5.2 Preparative Resolution of EMD 53986 174 5.8 Choosing a Technique for Preparative Enantioseparation 176 5.9 Conclusion 178 References 179 Part II Chiral Selectors 187 6 Polysaccharides 189 Weston Umstead, Takafumi Onishi, and Pilar Franco 6.1 Introduction 189 6.2 The Early Years 190 6.3 Polysaccharide Chiral Separation Mechanism 193 6.4 Coated Chiral Stationary Phases 197 6.5 Immobilized Chiral Stationary Phases 201 6.6 Applications of Polysaccharide- Derived CSPs 208 6.6.1 Analytical Applications 210 6.6.1.1 Pharmaceuticals 211 6.6.1.2 Agrochemicals 218 6.6.1.3 Food Analysis 219 6.6.2 Preparative Applications 220 6.7 Summation 224 References 224 7 Macrocyclic Antibiotics and Cyclofructans 247 Saba Aslani, Alain Berthod, and Daniel W. Armstrong 7.1 Introduction 247 7.2 Macrocyclic Glycopeptides Physicochemical Properties 248 7.3 Using the Chiral Macrocyclic Glycopeptides Stationary Phases 253 7.3.1 Mobile Phases and Chromatographic Modes 253 7.3.2 Chromatographic Enantioseparations 254 7.3.2.1 Amino Acids and Peptides 254 7.3.2.2 Chiral Compounds 257 7.3.2.3 Particle Structure 257 7.4 Using and Protecting Macrocyclic Glycopeptide Chiral Columns 260 7.4.1 Operating Conditions 260 7.4.2 Storage 261 7.5 Cyclofructans 261 7.5.1 Cyclofructan Structure and Properties 261 7.5.2 Chiral Separations with Cyclofructan- Based Stationary Phases 264 7.5.3 Cyclofructan Stationary Phases Used in the HILIC Mode 264 7.5.4 Cyclofructan Stationary Phases Used in Supercritical Fluid Chromatography 266 7.6 Conclusions 267 References 268 8 Cyclodextrins 273 Gerhard K. E. Scriba, Mari- Luiza Konjaria, and Sulaiman Krait 8.1 Introduction 273 8.2 Structure and Properties 274 8.3 Cyclodextrin Complexes 279 8.4 Application in Separation Science 288 8.4.1 Gas Chromatography 288 8.4.1.1 Types of Cyclodextrins 289 8.4.1.2 Types of Columns 289 8.4.1.3 Separation Mechanisms 291 8.4.1.4 Applications 293 8.4.2 Thin- Layer Chromatography 294 8.4.3 High- Performance Liquid Chromatography 294 8.4.3.1 Types of Columns 295 8.4.3.2 Types of Cyclodextrins 297 8.4.3.3 Separation Mechanisms 298 8.4.3.4 Applications 300 8.4.4 Supercritical Fluid Chromatography 300 8.4.5 Capillary Electromigration Techniques 301 8.4.5.1 Types of Cyclodextrins 301 8.4.5.2 Separation Mechanisms 302 8.4.5.3 Migration Modes and Enantiomer Migration Order Using CDs as Selectors 304 8.4.5.4 Applications 310 8.4.6 Membrane Technologies 312 8.5 Miscellaneous Applications 314 8.6 Conclusions and Outlook 315 References 315 9 Pirkle Type 325 Maria Elizabeth Tiritan, Madalena Pinto, and Carla Fernandes 9.1 Introduction 325 9.2 CSPs Developed by Pirkle’s Group: Chronological Evolution 327 9.3 Pirkle- Type CSPs Developed by Other Research Groups 334 9.4 Example of Applications in Analytical and Preparative Scales 340 9.4.1 Analytical Applications 341 9.4.2 Preparative Applications 349 9.5 Conclusions and Perspectives 349 References 350 10 Proteins 363 Jun Haginaka 10.1 Introduction 363 10.2 Preparation of Protein- and Glycoprotein- Based Chiral Stationary Phases 364 10.3 Types of Protein- and Glycoprotein- Based Chiral Stationary Phases 368 10.3.1 Proteins 368 10.3.1.1 Bovine Serum Albumin 368 10.3.1.2 Human Serum Albumin 370 10.3.1.3 Trypsin and α- Chymotrypsin 372 10.3.1.4 Lysozyme and Pepsin 372 10.3.1.5 Fatty Acid- Binding Protein 373 10.3.1.6 Penicillin G Acylase 375 10.3.1.7 Streptavidin 375 10.3.1.8 Lipase 376 10.3.2 Glycoproteins 376 10.3.2.1 Human α 1 - Acid Glycoprotein 376 10.3.2.2 Chicken Ovomucoid 377 10.3.2.3 Chicken α 1- Acid Glycoprotein 378 10.3.2.4 Avidin 380 10.3.2.5 Riboflavin- Binding Protein and Ovotransferrin 380 10.3.2.6 Cellobiohydrolase 381 10.3.2.7 Glucoamylase 383 10.3.2.8 Antibody (Immunoglobulin G) 385 10.3.2.9 Nicotinic Acetylcholine Receptor and Human Liver Organic Cation Transporter 387 10.4 Chiral Recognition Mechanisms on Proteinand Glycoprotein- Based Chiral Stationary Phases 387 10.4.1 Human Serum Albumin 387 10.4.2 Penicillin G Acylase 389 10.4.3 Human α 1- Acid Glycoprotein 390 10.4.4 Turkey Ovomucoid 392 10.4.5 Chicken α 1- Acid Glycoprotein 393 10.4.6 Cellobiohydrolase 395 10.4.7 Antibody 396 10.4.8 Nicotinic Acetylcholine Receptor and Human Liver Organic Cation Transporter 400 10.5 Conclusions 401 References 402 11 Chiral Stationary Phases Derived from Cinchona Alkaloids 415 Michael Lämmerhofer and Wolfgang Lindner 11.1 Introduction 415 11.2 Cinchona Alkaloid- Derived Chiral Stationary Phases 416 11.3 Chiral Recognition 420 11.4 Chromatographic Retention Mechanisms 424 11.4.1 Multimodal Applicability 424 11.4.2 Surface Charge of Cinchonan- Based CSPs 424 11.4.3 Retention Mechanisms and Models, and Method Development on Chiral WAX CSPs 427 11.4.4 Retention Mechanisms and Method Development on ZWIX CSPs 430 11.5 Structural Variants of Cinchona Alkaloid CSPs and Immobilization Chemistries 436 11.6 Cinchonan- Based UHPLC Column Technologies 442 11.7 Applications 446 11.7.1 Pharmaceutical and Biotechnological Applications 446 11.7.2 Biomedical Applications 453 11.8 Conclusions 460 References 460 Part III Methods for Stereochemical Elucidation 473 12 X- Ray Crystallography for Stereochemical Elucidation 475 Ademir F. Morel and Robert A. Burrow 12.1 Introduction 475 12.2 Absolute Structure and Absolute Configuration 476 12.3 Best Practices 482 12.4 Structure Validation 486 12.5 The Absolute Configuration of (+)- Lanatine A 486 12.6 The Absolute Configuration of the Diacetylated Form of Acrenol and the Acetylated Form of Humirianthol 488 12.7 The Absolute Configuration of Ester Form of Clemateol 491 12.8 Relative Configurations of Waltherione A, Waltherione B, and Vanessine 492 12.9 The Absolute Configuration of Condaline A 493 12.10 CSD Deposit Numbers 496 12.11 Conclusions and Future Directions 498 References 498 13 NMR for Stereochemical Elucidation 505 Xiaolu Li, Xiaoliang Yang, and Han Sun 13.1 Conventional NMR Methods for Stereochemical Elucidation 505 13.1.1 Determination of the Planar Structure Using 1D 1 H, 13 C NMR (DEPT), 2D HSQC, COSY, TOCSY, HMBC 506 13.1.2 Determination of Relative Configuration Using J- Couplings and NOEs/ROEs 507 13.1.2.1 Scalar Coupling 507 13.1.2.2 NOE/ROE 510 13.1.2.3 Examples of Stereochemical Elucidation Using J- Couplings and NOEs/ROEs 510 13.2 Determination of the Relative Configuration Using Anisotropic NMR- Based Methods 516 13.2.1 Basic Principles of Anisotropic NMR Parameters 517 13.2.2 Alignment Media 518 13.2.2.1 Preparation of Anisotropic Sample with PMMA Gel 520 13.2.2.2 Preparation of Anisotropic Sample with AAKLVFF 521 13.2.3 Acquisition of the Anisotropic NMR Data 522 13.2.4 Computational Approaches for Analyzing Anisotropic NMR Data 525 13.2.5 Successful Examples of Determination of Relative Configuration of Challenging Molecules Using Anisotropic NMR 528 13.3 Determination of the Relative Configuration Using DP 4 Probability and CASE- 3D 529 13.4 Determination of the Absolute Configuration Using a Combination of NMR Spectroscopy and Chiroptical Spectroscopy 533 13.5 Determination of the Absolute Configuration Using NMR Alone 534 13.5.1 Mosher Ester Analysis 535 13.5.2 Other Chiral Derivatizing Agents 536 13.6 Future Perspective 536 References 537 14 Absolute Configuration from Chiroptical Spectroscopy 551 Fernando Martins dos Santos Junior and João Marcos Batista Junior 14.1 Introduction 551 14.2 Chiroptical Methods 554 14.2.1 Optical Rotation and Optical Rotatory Dispersion 554 14.2.1.1 Instrumentation 556 14.2.1.2 Measurements 557 14.2.2 Electronic Circular Dichroism 558 14.2.2.1 Instrumentation 560 14.2.2.2 Measurements 561 14.2.3 Vibrational Circular Dichroism and Raman Optical Activity 561 14.2.3.1 Instrumentation 563 14.2.3.2 Measurements 565 14.2.4 Simulation of Chiroptical Properties 567 14.2.4.1 Common Theoretical Steps 568 14.2.4.2 OR and ORD Simulations 570 14.2.4.3 ECD Simulations 572 14.2.4.4 VCD and ROA Simulations 573 14.2.5 Examples of Application 575 14.2.5.1 OR 575 14.2.5.2 ORD 577 14.2.5.3 ECD 578 14.2.5.4 VCD 579 14.2.5.5 ROA 581 14.2.5.6 Association of Different Chiroptical Methods 582 14.3 Concluding Remarks 585 References 586 Index 593
£170.10
John Wiley & Sons Inc Perspectives on Structure and Mechanism in
Book SynopsisPERSPECTIVES ON STRUCTURE AND MECHANISM IN ORGANIC CHEMISTRY Beyond the basics physical organic chemistry textbook, written for advanced undergraduates and beginning graduate students Based on the author's first-hand classroom experience, Perspectives on Structure and Mechanism in Organic Chemistry uses complementary conceptual models to give new perspectives on the structures and reactions of organic compounds, with the overarching goal of helping students think beyond the simple models of introductory organic chemistry courses. Through this approach, the text better prepares readers to develop new ideas in the future. In the 3rd Edition, the author thoroughly updates the topics covered and reorders the contents to introduce computational chemistry earlier and to provide a more natural flow of topics, proceeding from substitution, to elimination, to addition. About 20% of the 438 problems have been either replaced or updated, with answers available in the companion solutions manual. To remind students of the human aspect of science, the text uses the names of investigators throughout the text and references material to original (or accessible secondary or tertiary) literature as a guide for students interested in further reading. Sample topics covered in Perspectives on Structure and Mechanism in Organic Chemistry include: Fundamental concepts of organic chemistry, covering atoms and molecules, heats of formation and reaction, bonding models, and double bondsDensity functional theory, quantum theory of atoms in molecules, Marcus Theory, and molecular simulationsAsymmetric induction in nucleophilic additions to carbonyl compounds and dynamic effects on reaction pathwaysReactive intermediates, covering reaction coordinate diagrams, radicals, carbenes, carbocations, and carbanionsMethods of studying organic reactions, including applications of kinetics in studying reaction mechanisms and Arrhenius theory and transition state theory A comprehensive yet accessible reference on the subject, Perspectives on Structure and Mechanism in Organic Chemistry is an excellent learning resource for students of organic chemistry, medicine, and biochemistry. The text is ideal as a primary text for courses entitled Advanced Organic Chemistry at the upper undergraduate and graduate levels.Table of ContentsPreface xi Chapter 1 Fundamental Models of Organic Chemistry 1 1.1 Atoms and Molecules 1 Basic Concepts 1 Molecular Dimensions 5 1.2 Heats of Formation and Reaction 8 Experimental Determination of Heats of Formation 8 Bond Increment Calculation of Heats of Formation 10 Group Increment Calculation of Heats of Formation 11 Heats of Formation and the Concept of Protobranching 13 Homolytic and Heterolytic Bond Dissociation Energies 15 1.3 Bonding Models 18 Electronegativity and Bond Polarity 20 Complementary Theoretical Models of Bonding 23 Pictorial Representations of Bonding Concepts 27 sp3 Hybridization 28 Are There sp3 Hybrid Orbitals in Methane? 30 Hybridization and Molecular Geometry 34 Variable Hybridization 35 1.4 Complementary Models for the Double Bond 41 The σ,π Description of Ethene 41 The Bent Bond Description of Ethene 42 Predictions of Physical Properties with the Two Models 42 1.5 The Role of Complementary Models in Organic Chemistry 46 Problems 47 Chapter 2 Introduction to Computational Chemistry 53 2.1 Hückel Molecular Orbital Theory 53 Correlation of Physical Properties with Results of HMO Calculations 63 Other Parameters Generated Through HMO Theory 67 Properties of Odd Alternant Hydrocarbons 69 The Frost Circle 74 2.2 Aromaticity 75 Benzene 77 Other Aromatic Systems 81 Polycyclic Conjugated Systems 85 Larger Annulenes 90 Dewar Resonance Energy and Absolute Hardness 93 2.3 Contemporary Computational Methods 95 Extended Hückel Theory 95 Semiempirical Methods 96 Ab Initio Theory 97 2.4 Localized Molecular Orbitals 100 Perturbational Molecular Orbital Theory 104 Atoms in Molecules 108 2.5 Density Functional Theory 112 2.6 Another Look at Valence Bond Theory 114 Resonance Structures and Resonance Energies 114 Interpreting Computational Results 117 Problems 119 Chapter 3 Stereochemistry 127 3.1 Representations of Three-Dimensional Structures 127 3.2 Stereoisomerism 130 Isomerism 130 Symmetric, Asymmetric, Dissymmetric, and Nondissymmetric Molecules 133 Fischer Projections 146 Additional Stereochemical Designations 149 3.3 Physical Manifestations of Chirality 159 Optical Activity 159 Configuration and Optical Activity 161 Other Physical Properties of Stereoisomers 166 3.4 Stereotopicity 167 Stereochemical Relationships of Substituents 167 Chirotopicity and Stereogenicity 171 Problems 172 Chapter 4 Molecular Geometry and Steric Energy 183 4.1 Designation of Molecular Conformation 183 4.2 Conformational Analysis 187 Torsional Strain 187 van der Waals Strain 191 Angle Strain and Baeyer Strain Theory 193 Application of Conformational Analysis to Cycloalkanes 194 Conformational Analysis of Substituted Cyclohexanes 198 4.3 Molecular Mechanics 204 4.4 Anomeric Effect 221 4.5 Strain and Molecular Stability 225 Problems 237 Chapter 5 Reactive Intermediates 243 5.1 Reaction Coordinate Diagrams 243 5.2 Radicals 244 Early Evidence for the Existence of Radicals 244 Detection and Characterization of Radicals 246 Structure and Bonding of Radicals 251 Thermochemical Data for Radicals 253 Generation of Radicals 255 Radical Chain Reactions 256 5.3 Carbenes 263 Structure and Geometry of Carbenes 263 Generation of Carbenes 267 Reactions of Carbenes 268 5.4 Carbocations 272 Carbonium Ions and Carbenium Ions 272 Structure and Geometry of Carbocations 274 The 2-Norbornyl Cation 281 Carbocation Rearrangements 283 Radical Cations 285 5.5 Carbanions 290 Generation of Carbanions 294 Stability of Carbanions 296 Reactions of Carbanions 296 5.6 Choosing Models of Reactive Intermediates 298 Problems 299 Chapter 6 Determining Reaction Mechanisms 305 6.1 Reaction Mechanisms 305 6.2 Methods to Determine Reaction Mechanisms 306 Identification of Reaction Products 306 Determination of Intermediates 306 Crossover Experiments 311 Isotopic Labeling 313 Stereochemical Studies 314 Solvent Effects 315 Computational Studies 317 6.3 Applications of Kinetics in Studying Reaction Mechanisms 319 6.4 Arrhenius Theory and Transition State Theory 326 6.5 Reaction Barriers and Potential Energy Surfaces 337 6.6 Kinetic Isotope Effects 348 Primary Kinetic Isotope Effects 349 Secondary Kinetic Isotope Effects 354 Tunneling and Isotope Effects 359 Solvent Isotope Effects 362 6.7 Substituent Effects 363 6.8 Linear Free Energy Relationships 368 Problems 383 Chapter 7 Acid and Base Catalysis of Organic Reactions 393 7.1 Acidity and Basicity of Organic Compounds 393 Acid–Base Measurements in Solution 393 Acid–Base Reactions in the Gas Phase 402 Comparison of Gas Phase and Solution Acidities 408 Acidity Functions 410 7.2 Acid and Base Catalysis of Chemical Reactions 413 Specific Acid Catalysis 413 General Acid Catalysis 414 Brønsted Catalysis Law 417 7.3 Acid and Base Catalysis of Reactions of Carbonyl Compounds and Carboxylic Acid Derivatives 418 Addition to the Carbonyl Group 418 Enolization of Carbonyl Compounds 422 Hydrolysis of Acetals 426 Acid-Catalyzed Hydrolysis of Esters 428 Alkaline Hydrolysis of Esters 431 Hydrolysis of Amides 437 Problems 441 Chapter 8 Substitution Reactions 449 8.1 Introduction 449 8.2 Nucleophilic Aliphatic Substitution 450 8.3 The SN1 Reaction 453 Kinetics 453 Structural Effects in SN1 Reactions 454 Solvent Polarity and Nucleophilicity 455 Solvated Ions and Ion Pairs 459 Anchimeric Assistance in SN1 Reactions 464 Nonclassical Carbocations in SN1 Reactions 469 8.4 The SN2 Reaction 471 Stereochemistry 471 Solvent Effects 473 Substrate Effects 477 8.5 Quantitative Measures of Nucleophilicity 480 Brønsted Correlations 481 Hard–Soft Acid–Base Theory and Nucleophilicity 482 Edwards Equations 483 Swain-Scott Equation 484 Mayr Equations 485 The α-Effect 488 Leaving Group Effects in SN2 Reactions 489 Aliphatic Substitution and Single Electron Transfer 490 8.6 Electrophilic Aromatic Substitution 495 The SEAr Reaction 495 Quantitative Measurement of SEAr Rate Constants: Partial Rate Factors 498 Lewis Structures as Models of Reactivity in SEAr Reactions 500 8.7 Nucleophilic Aromatic and Vinylic Substitution 504 Nucleophilic Aromatic Substitution 504 Nucleophilic Vinylic Substitution 509 8.8 Substitution Involving Benzyne Intermediates 511 8.9 Radical-Nucleophilic Substitution 518 8.10 The Impermanence of Mechanistic Labels 521 Problems 521 Chapter 9 Elimination Reactions 529 9.1 Introduction 529 9.2 Dehydrohalogenation and Related 1,2-Elimination Reactions 534 Potential Energy Surfaces for 1,2-Elimination 534 Competition Between Substitution and Elimination 540 Stereochemistry of 1,2-Elimination Reactions 541 Elimination Reactions to Produce Alkynes 547 Regiochemistry of 1,2-Elimination Reactions 548 9.3 Other 1,2-Elimination Reactions 558 Dehalogenation of Vicinal Dihalides 558 Dehydration of Alcohols 561 Deamination of Amines 568 Pyrolytic Eliminations 572 Problems 578 Chapter 10 Addition Reactions 587 10.1 Introduction 587 10.2 Addition of Halogens to Alkenes 588 Electrophilic Addition of Bromine to Alkenes 588 Role of Charge-Transfer Complexes in Bromine Addition Reactions 592 Kinetics of Bromine Addition Reactions 593 Solvent Effects in Bromine Additions 596 Reversibility of Bromine Addition 598 Intermediates in the Addition of Bromine to Alkyl-Substituted Alkenes 599 Intermediates in the Addition of Bromine to Aryl-Substituted Alkenes 604 Summary of Bromine Addition 608 Addition of Other Halogens to Alkenes 609 10.3 Other Addition Reactions 618 Addition of Hydrogen Halides to Alkenes 618 Hydration of Alkenes 625 Oxymercuration 628 Hydroboration 632 Epoxidation 637 Electrophilic Addition to Alkynes and Cumulenes 639 Nucleophilic Addition to Alkenes and Alkynes 647 Nucleophilic Addition to Carbonyl Compounds 651 Problems 656 Chapter 11 Pericyclic Reactions 661 11.1 Introduction 661 11.2 Electrocyclic Transformations 665 Definitions and Selection Rules 665 MO Correlation Diagrams 670 State Correlation Diagrams 675 11.3 Sigmatropic Reactions 678 Selection Rules for Sigmatropic Reactions 679 Other Examples of Sigmatropic Reactions 687 11.4 Cycloaddition Reactions 691 Introduction 691 Ethene Dimerization 692 The Diels–Alder Reaction 694 Selection Rules for Cycloaddition Reactions 698 11.5 Other Pericyclic Reactions 705 Cheletropic Reactions 705 Double Group Transfer Reactions 707 Ene Reactions 709 11.6 A General Selection Rule for Pericyclic Reactions 711 11.7 Alternative Conceptual Models for Pericyclic Reactions 713 Frontier Molecular Orbital Theory 713 Hückel and Möbius Aromaticity of Transition Structures 719 Synchronous and Nonsynchronous Pericyclic Reactions 725 Potential Energy Surfaces and Ambimodal Reactions 729 11.8 Reaction Dynamics and Potential Energy Surfaces 729 Problems 735 Chapter 12 Organic Photochemistry 745 12.1 Energy and Electronic States 745 12.2 Photophysical Processes 747 Designation of Spectroscopic Transitions 748 Selection Rules for Radiative Transitions 754 Fluorescence and Phosphorescence 756 Energy Transfer and Electron Transfer 759 12.3 Photochemical Kinetics 763 Actinometry and Quantum Yield Determinations 763 Rate Constants for Unimolecular Processes 764 Transient Detection and Monitoring 765 Bimolecular Decay of Excited States: Stern–Volmer Kinetics 768 12.4 Physical Properties of Excited States 770 Acidity and Basicity in Excited States 770 Bond Angles and Dipole Moments of Excited-State Molecules 774 12.5 Representative Photochemical Reactions 777 Photochemical Reactions of Alkenes and Dienes 778 Photochemical Reactions of Carbonyl Compounds 790 Photochemical Reactions of α,ß-Unsaturated Carbonyl Compounds 798 Photochemical Reactions of Aromatic Compounds 800 Photosubstitution Reactions 802 σ Bond Photodissociation Reactions 803 Singlet Oxygen and Organic Photochemistry 808 12.6 Applications of Organic Photochemistry 811 Problems 822 References for Selected Problems 831 Index 837
£111.56
John Wiley & Sons Inc Solutions Manual for Perspectives on Structure
Book SynopsisSOLUTIONS MANUAL FOR PERSPECTIVES ON STRUCTURE AND MECHANISM IN ORGANIC CHEMISTRY Based on the author's first-hand classroom experience, this solutions manual complements the 3rd edition of Perspectives on Structure and Mechanism in Organic Chemistry. The solutions to the 438 textbook problems help students increase their understanding of physical organic chemistry, and more than 550 references stimulate their engagement with the chemical literature.Table of ContentsChapter 1 Fundamental Models of Organic Chemistry 1 Chapter 2 Introduction to Computational Chemistry 11 Chapter 3 Stereochemistry 31 Chapter 4 Molecular Geometry and Steric Energy 49 Chapter 5 Reactive Intermediates 57 Chapter 6 Determining Reaction Mechanisms 65 Chapter 7 Acid and Base Catalysis of Organic Reactions 73 Chapter 8 Substitution Reactions 81 Chapter 9 Elimination Reactions 93 Chapter 10 Addition Reactions 105 Chapter 11 Pericyclic Reactions 117 Chapter 12 Organic Photochemistry 133
£36.05
John Wiley & Sons Inc Organic Reactions Volume 110
Book SynopsisTable of Contents1. Radical Allylation, Vinylation, Allenylation, Alkynylation, and Propargylation Reactions Using Tin Reagents 1Ian J. Rosenstein 2. Enantioselective Epoxide Opening 655Makoto Nakajima, Shunsuke Kotani, and Masaharu Sugiura Cumulative Chapter Titles by Volume 903 Author Index, Volumes 1–110 923 Chapter and Topic Index, Volumes 1–110 931
£289.80
John Wiley & Sons Inc Photocatalysts and Electrocatalysts in Water
Book SynopsisPhotocatalysts and Electrocatalysts in Water Remediation Comprehensive resource describing the fundamentals, synthesis, and commercial applications of photocatalysts and electrocatalysts in water decontamination Photocatalysts and Electrocatalysts in Water Remediation introduces the fundamentals of both photo- and electro-catalysts and highlights the potentials of photo- and electro-catalysis towards water decontamination, covering strategies to improve photo- and electro-catalytic efficacies, functions of photo- and electro-catalysts and involved chemical reactions, and challenges and recent developments in the field, with additional discussion of both lab-scale and commercial-scale materials and processes. As a forward-thinking resource, the text also discusses the scope of further research on photo-, electro- and electrophoto-catalysts. Edited by three highly qualified professionals, with significant experience in the field, the text is further enrichTable of ContentsPreface ix About the Editors xi List of Contributors xiii Acknowledgements xv 1 Fundamentals and Functional Mechanisms of Photocatalysis in Water Treatment 1 1.1 Introduction 1 1.2 Different Photocatalytic Materials for Water Treatment 2 1.3 In-depth Mechanisms of Photocatalysis 9 1.4 Visible Light Driven Photocatalysts for Water Decontamination 20 1.5 Summary 25 2 Different Synthetic Routes and Band Gap Engineering of Photocatalysts 39 2.1 Introduction 39 2.2 Synthesis of Photocatalysts 40 2.3 Properties of Ideal Photocatalytic Material 57 2.4 Engineering Photocatalytic Properties 58 2.5 Energy Bandgap 59 2.6 Engineering the Desired Band Gap 64 2.7 Photocatalytic Mechanisms, Schemes and Systems 69 2.8 Summary and Perspectives 71 3 Photocatalytic Decontamination of Organic Pollutants from Water 81 3.1 Introduction 81 3.2 Photocatalytic Degradation Mechanisms of Organic Contaminants 82 3.3 Advanced Photocatalytic Materials for Decontamination of Organic Pollutants 83 3.4 Solar/Visible-light Driven Photocatalytic Decontamination of Organic Pollutants 85 3.5 Emerging Scientific Opportunities of Photocatalysts in Removal of Organic Pollutants 87 3.6 Limitations of Photocatalytic Decontamination and Key Mitigation Strategies 95 3.7 Summary and Future Directions 96 4 Photocatalytic Removal of Heavy Metal Ions from Water 105 4.1 Introduction 105 4.2 Mechanistic Insights on Photocatalytic Removal of Heavy Metal Ions 110 4.3 Solar/Visible-light Driven Photocatalysts for the Removal of Heavy Metal Ions 113 4.4 Selective Heavy Metal Ion Removal by Semiconductor Photocatalysts 123 4.5 Major Drawbacks and Key Mitigation Strategies 125 4.6 Summary and Future Directions 126 5 Smart Photocatalysts in Water Remediation 135 5.1 Introduction 135 5.2 Advances in the Development of Visible-light Driven Photocatalysts 138 5.3 Advances in Photocatalyst Immobilization and Supports 142 5.4 Advances in Nonimmobilized Smart Photocatalysts 144 5.5 Advances in Improving the Efficiency of Light Delivery 149 5.6 Advances in Biomaterials for Designing Smart Photocatalysts 157 5.7 Advances Toward Improving Photocatalytic Activity via External Stimuli 159 5.8 Advances in Inhibiting the Photocorrosion of Semiconductor-based Photocatalysts 164 5.9 Advances in Recycling Photocatalysts: Assessing the Photocatalyst Life Cycle 166 5.10 Summary, Future Challenges, and Prospects for Further Research 167 6 Fundamentals and Functional Mechanisms of Electrocatalysis in Water Treatment 189 6.1 Introduction 189 6.2 Electrocatalysis Treatment 190 6.3 Properties and Characteristics of Different Electrocatalysis Techniques 192 6.4 Case Studies and Successful Approaches 202 6.5 Conclusion 217 7 Different Synthetic Routes of Electrocatalysts and Fabrication of Electrodes 229 7.1 Introduction 229 7.2 Fundamental Principles of Alkaline Water Oxidation 230 7.3 Electrochemical Evaluating Parameters of Electrocatalysts for OER Performance 231 7.4 Electrocoagulation 233 7.5 Electroflotation 233 7.6 Electrocoagulation/flotation 233 7.7 Electro-oxidation in Wastewater Treatment 233 7.8 Doped Diamond Electrodes 234 7.9 Conclusion 235 8 Electrocatalytic Degradation of Organic Pollutants from Water 241 8.1 Introduction 241 8.2 Principles and Fundamental Aspects of Electrooxidation 242 8.3 Electrode Materials and Cell Configuration 244 8.4 Performance Assessment Indicators and Operating Variables 250 8.5 Electrochemical Filtering Process: A Hybrid Process Based on Electrooxidation and Filtering 253 8.6 Integration of Electrooxidation-based Processes in Water/Wastewater Treatment Technological Flow 259 9 Electrocatalytic Removal of Heavy Metal Ions from Water 275 9.1 Introduction 275 9.2 Fundamentals 277 9.3 Advantages and Disadvantages of the Electrocatalytic Approach 283 9.4 Summary 284 10 Combined Photoelectrocatalytic Techniques in Water Remediation 289 10.1 Introduction 289 10.2 Photoelectrocatalysts for Treatment of Water Contaminants 292 10.3 Simultaneous Removal of Organic and Inorganic Pollutants 302 10.4 Conclusions and Perspective 304 Index 311
£144.00
John Wiley & Sons Inc Organic Reactions Volume 113
Book SynopsisA carefully curated review of the scientific literature, Volume 113 of Organic Reactions presents critical discussions of widely used organic reactions or particular steps of a reaction. The material is treated from a preparative viewpoint, with emphasis on limitations, interfering influences, effects of structure and the selection of experimental techniques. The work includes tables that contain all possible examples of the reaction under consideration. Detailed procedures illustrate the significant modifications of each method. Launched in 1942, the Organic Reactions series today is a leading secondary- and tertiary-level source for organic chemists across the world.Table of Contents1. Transition-Metal-Catalyzed Alkyl–Alkyl Cross-Coupling Reactions 1 Takanori Iwasaki and Nobuaki Kambe 2. Hydrozirconation of Alkynes 457 John A Milligan, Courtney V Hammill, Desirae L Crocker, and Peter Wipf Cumulative Chapter Titles by Volume 795 Author Index, Volumes 1–113 817
£269.10
John Wiley and Sons Ltd Structure and Reactivity in Organic Chemistry
Book SynopsisThe jump from an understanding of organic chemistry at lower undergraduate level to that required at postgraduate level or in industry can be difficult. Many advanced textbooks contain a level of detail which can obscure the essential mechanistic framework that unites the huge range of facts of organic chemistry.Trade Review“The author's approach is methodical and clever in that he brings relevance to protecting group chemistry under each class of reactions.” (CHOICE) "It will serve as a good reference source for any course that deals with physical organic chemistry." (CHOICE, January 2009) "An extremely well thought out and well presented book that achieves the author’s stated aims and deserves to be on any practising organic chemist’s shelf." (The Higher Education Academy Physical Sciences Centre, December 2008) "This book will be extremely useful as a guide to the essentials of modern organic chemistry, provided that you have a very good knowledge of organic chemistry or an excellent teacher to guide you through it." (Angewandte Chemie International Edition, December 22, 2008)Table of ContentsPreface xi 1 Bonding 1 1.1 Atomic structure 1 1.1.1 The chemical bond 1 1.1.2 The periodic table 1 1.1.3 Valence electrons 3 1.1.4 Lewis structures 3 1.1.5 Conventions for drawing structures 5 1.1.6 Atomic orbital theory 6 1.1.7 Molecular orbital theory 7 1.2 Covalent bonding 10 1.2.1 Bonding in hydrocarbons 11 1.2.2 Bonding in compounds containing heteroatoms 12 1.2.3 Bonding in common functional groups 12 1.2.4 Electronic effects 14 1.2.5 Steric effects 18 1.2.6 Stereoelectronic effects 18 1.2.7 Double bond equivalents 20 2 Structure 21 2.1 Configuration 21 2.1.1 Geometrical isomerism 22 2.1.2 Optical isomerism 23 2.1.3 Representations of stereoisomers 25 2.1.4 Molecules with one stereogenic centre 27 2.1.5 Molecules with more than one stereogenic centre 27 2.1.6 Molecules with more than one stereogenic centre which are not optically active 28 2.1.7 Optically active molecules without stereogenic centres: molecular asymmetry 29 2.1.8 Asymmetric heteroatoms 30 2.2 Conformation 31 2.2.1 Representation of conformers 31 2.2.2 Open-chain compounds 31 2.2.3 Ring compounds 33 2.3 Summary of stereochemical relationships 39 2.4 Naturally occurring chiral compounds 39 2.5 Asymmetric synthesis 41 2.5.1 Enantioselective synthesis 41 2.5.2 Diastereoselective synthesis 43 2.5.3 Methods for the determination of enantiomeric purity 43 3 Reactivity 47 3.1 Thermodynamics 47 3.1.1 Gibbs free energy 47 3.1.2 Enthalpy 48 3.1.3 Entropy 50 3.1.4 Chemical equilibrium 52 3.2 Kinetics 54 3.2.1 Rates of reaction 54 3.2.2 Reactions with competing steps 57 3.2.3 Overcoming activation energy barriers 58 3.3 Reaction mechanism 60 3.3.1 What is reactivity? 60 3.3.2 Lewis acids and bases: ‘philicity’ 60 3.3.3 Polarisability effects: Hard–Soft Acid–Base theory 61 3.3.4 Curly (‘curved’) arrows 63 3.4 Classes of reaction mechanism 66 3.4.1 Polar mechanisms 66 3.4.2 Radical mechanisms 67 3.4.3 Pericyclic mechanisms 67 3.4.4 Ligand coupling reaction mechanisms 67 3.5 Principle of microscopic reversibility 68 3.6 Selectivity of reactions 69 3.7 Solvents in organic chemistry 71 3.8 Redox reactions in organic chemistry 72 4 Intermediates 77 4.1 Carbocations 77 4.1.1 Structure 77 4.1.2 Factors stabilising carbocations 77 4.1.3 Generation of carbocations 81 4.1.4 Rearrangements of carbocations 82 4.2 Carbanions 82 4.2.1 Structure 82 4.2.2 Carbanions derived from simple alkanes 84 4.2.3 Factors stabilising carbanions 85 4.3 Carbanions with covalent character 88 4.3.1 Grignard reagents (RMgX) 88 4.3.2 Organolithium reagents (RLi) 89 4.3.3 Organocadmium reagents 89 4.4 Radicals 90 4.4.1 Structure 90 4.4.2 Factors stabilising radicals 90 4.4.3 Generation of radicals 92 4.5 Carbenes 94 4.5.1 Stability and structure 94 4.5.2 Generation of carbenes 95 4.6 Benzynes 96 4.6.1 Stability and structure 96 4.6.2 Generation of benzynes 97 4.7 Ketenes 98 4.7.1 Stability and structure 98 4.7.2 Generation of ketenes 98 5 Acidity and Basicity 99 5.1 Lowry–Brønsted Acid–Base theory 99 5.2 Organic acidity 100 5.2.1 Organic acids 100 5.3 Organic basicity 111 5.3.1 Organic bases 112 6 Nucleophilic Substitution 117 6.1 The S N 1 reaction 117 6.1.1 Factors affecting the S N 1 reaction 118 6.2 The S N 2 reaction 123 6.2.1 Factors enhancing the S N 2 reaction 124 6.3 Synthetic applications of nucleophilic substitution reactions 128 6.3.1 Protecting-group chemistry 128 6.3.2 Stereocontrolled alkylation reactions 131 7 Addition Reactions 139 7.1 Electrophilic addition reactions 139 7.1.1 Addition of halogens 139 7.1.2 Addition of hydrogen halides 141 7.1.3 Addition of hydrogen halides to conjugated dienes 143 7.1.4 Addition of diborane (hydroboration) 143 7.1.5 Addition of hydrogen 147 7.1.6 Addition of oxygen 148 7.1.7 Addition of carbon 153 7.2 Nucleophilic addition reactions 153 7.2.1 Irreversible nucleophilic addition 154 7.2.2 Irreversible nucleophilic conjugate addition 159 7.2.3 Reversible nucleophilic addition 160 7.3 Additions to electron-deficient alkenes 165 7.4 Additions of ketenes 165 7.5 Synthetic applications 166 8 Elimination Reactions 169 8.1 Eliminations 169 8.1.1 E 1 reactions 169 8.1.2 E 1 CB reactions 169 8.1.3 E 2 reactions 170 8.1.4 Eliminations leading to isomeric products 173 8.1.5 Competition between substitution and elimination 175 8.1.6 The leaving group 176 8.2 Oxidation processes 178 8.3 Eliminations leading to carbenes and nitrenes 181 8.4 Eliminations of phosphorus 182 8.5 Eliminations of sulfur and selenium 182 8.6 Eliminations in protecting-group chemistry 184 9 Aromatic Substitution 189 9.1 Aromaticity 189 9.1.1 Benzene 189 9.1.2 Heteroaromatics 189 9.2 Reactions 191 9.2.1 Acidity and basicity 191 9.2.2 Electrophilic aromatic substitution 191 9.2.3 Orientation effects in electrophilic aromatic substitution (S E Ar) 202 9.2.4 o-Lithiation 205 9.2.5 Nucleophilic aromatic substitution 206 9.2.6 Arene chromium tricarbonyl complexes 211 10 Sequential Addition and Elimination Reactions 213 10.1 Addition–elimination reactions 213 10.1.1 Addition of hydride 220 10.1.2 Addition of heteroatom nucleophiles 221 10.1.3 Addition of carbon nucleophiles 222 10.1.4 Addition of phosphorus nucleophiles 225 10.2 Addition–elimination reactions in conjugated systems 230 10.3 Addition–elimination reactions in heterocyclic systems 230 10.4 Addition–elimination reactions in ring-closing metathesis 231 10.5 Addition–elimination reactions in deprotections 234 11 Radical Reactions 237 11.1 Generation 237 11.2 Reactions 237 11.2.1 Termination 237 11.2.2 Propagation 238 11.2.3 Substitution 239 11.2.4 Addition reactions 242 11.2.5 Fragmentation 249 11.2.6 Rearrangement 250 11.3 Synthetic utility 255 12 Ligand Coupling Reactions 263 12.1 Palladium-mediated couplings 263 12.1.1 Palladium-mediated coupling processes 264 12.1.2 Heck coupling 271 12.1.3 Allylic coupling processes 273 12.2 Ligand coupling processes mediated by other elements 275 12.2.1 Copper 276 12.2.2 Magnesium 277 12.2.3 Lead 279 13 Pericyclic Reactions 283 13.1 Molecular orbitals and the FMO approach 283 13.2 Pericyclic reactions 284 13.2.1 Electrocyclic reactions 285 13.2.2 Cycloaddition reactions 287 13.2.3 Sigmatropic reactions 293 13.3 Synthetic applications of pericyclic reactions 296 Index 303
£46.50
