Catalysis Books

Book SynopsisVolume 5 in the Catalysts for Fine Chemical Synthesis series describes new procedures for the regio- and stereo-controlled transformations of compounds involving oxidation or reduction reactions. It describes a wide range of catalysts, including organometallic systems, biocatalysts and biomimetics.Table of ContentsCHAPTER 1: Industrial Catalysts for Regio- or Stereo- selective Oxidations and Reductions. A Review of Key Technologies and Targets. J. Whittall CHAPTER 2: Asymmetric Hydrogenation of Alkenes, Enones, Ene-esters and Ene-Acids 2.1: (S)-2,2'- Bis{[di(4-methoxyphenyl)phosphinyl]oxy}-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation I. Gergely, C. Hegeds and J. Bakos. 2.2: Synthesis and Application of Phosphinite Oxazoline Iridium Complexes for the Asymmetric Hydrogenation of Alkenes F. Menges and A. Pfaltz. 2.3: Synthesis and Application of Heterocyclic Phosphine Oxazoline (HetPHOX) Iridium Complexes for the Asymmetric Hydrogenation of Alkenes F. Menges and P.G. Cozzi. 2.4: (R)-2,2',6,6'- Tetramethoxy-bis[di(3,5-dimethylphenyl)phosphino]-3,3'-bipyridine [(R)-Xyl-P-Phos] as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation of a-Dehydroamino Acids J. Wu and A.S.C. Chan. 2.5: (R,R)-2,3-Bis(tert-butylmethylphosphine)quinoxaline (Quinox P*) as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation of Prochiral Amino Acid and Amine Derivatives T. Imamoto and A. Koide. 2.6: Rhodium-Catalysed Asymmetric Hydrogenation of Indoles R. Kuwano and M. Sawamura. CHAPTER 3: Asymmetric Reduction of Ketones 3.1: (R,R)-Bis(diphenylphosphino)-1,3-diphenylpropane as a Versatile Ligand for Enantioselective Hydrogenations N. Dubrovina and A. Borner. 3.2: Synthesis of Both Enantiomers of 1-Phenylethanol by Reduction of Acetophenone with Geotrichum candidum IFO 5767 K. Nakamura, M. Fujii and Y. Ida. 3.3: Titanocene-Catalysed Reduction of Ketones in the Presence of Water. A Convenient Procedure for the Synthesis of Alcohols by Free-Radical Chemistry A. Rosales, J.M. Cuerva and J.E. Oltra. 3.4: Xyl-TetraPHEMP: A Highly Efficient Biaryl Ligand in the [Diphosphine RuCl2-diamine]-Catalysed Hydrogenation of Simple Aromatic Ketones P.H. Moran, J.P. Henschke, A. Zanotti-Gerosa and I C. Lennon. 3.5: N-Arenesulfonyl- and N-Alkylsulfamoyl-1,2-diphenylethylenediamine Ligands for Ruthenium-Catalysed Asymmetric Transfer Hydrogenation of Activated Ketones M.S. Stephan and B. Mohar. 3.6: The Synthesis and Application of BrXUPHOS: A Novel Monodentate Phosphorus Ligand for the Asymmetric Hydrogenation of Ketones M. Wills, Y. Xu, G. Docherty and G. Woodward. 3.7: In Situ Formation of Ligand and Catalyst: Application in Ruthenium-Catalysed Enantioselective Reduction of Ketones J. Wettergren and H. Adolfsson. 3.8: SYNPHOS and DIFLUORPHOS as Ligands for Ruthenium-Catalysed Hydrogenation of Alkenes and Ketones S. Jeulin, V. Ratovelomanana-Vidal and J-P. Genet. 3.9: An Arene Ruthenium Complex with Polymerizable Side-chains for the Synthesis of Immobilised Catalysts E. Burri, S.B. Wendicke, K. Severin. 3.10: Selective Reduction of Carbonyl Group in beta, gamma- Unsaturated alpha- Ketoesters by Transfer Hydrogenation with Ru-(para-cymene) (TsDPEN) M. Guo, D. Li, Y. Sun and Z. Zhang. 3.11: Preparation of Polymer-Supported Ru-TsDPEN Catalysts and their Use for the Enantioselective Synthesis of (S)-Fluoxetine L. Chai, Y. Li and Q. Wang. 3.12: Polymer-Supported Chiral Sulfonamide-Catalysed Reduction of B-Keto Nitrile: a Practical Synthesis of (R)-Fluoxetine G.Wang and G. Zhao. CHAPTER 4: Imine Reduction and Reductive Amination 4.1: Metal-Free Reduction of Imines: Enantioselective Bronsted Acid-Catalysed Transfer Hydrogenation using Chiral BINOL-Phosphates as Catalysts M. Rueping, E. Sugiono, C. Azap and T. Theissmann. 4.2: Metal-Free Bronsted Acid-Catalysed Transfer Hydrogenation: Enantioselective Synthesis of Tetrahydroquinolines M. Rueping , T. Theissmann and A. P. Antonchick. 4.3: A Highly Stereoselective Synthesis of 3a-Amino-23,24-bisnor-5a-cholane via Reductive Amination S. N. Khan, N.J. Cho and H-S. Kim. CHAPTER 5: Oxidation of Primary and Secondary Alcohols 5.1: Copper (II)-Catalysed Oxidation of Primary Alcohols to Aldehydes with Atmospheric Oxygen S. Jammi and T. Punniyamurthy. 5.2: Solvent-free Dehydrogenation of Secondary Alcohols in the Absence of Hydrogen Abstractors using Robinson's Catalyst G.B.W.L. Ligthart, R.H. Meijer, J. v. Buijtenen, J. Meuldijk, J.A.J.M. Vekemans and L. A. Hulshof. 5.3: 2-Iodoxybenzoic Acid (IBX)/ n-Bu4NBr/ CH2Cl2-H2O: a Mild System for the Selective Oxidation of Secondary Alcohols K. Kittigowittana, M. Pohmakotr, V. Reutrakul and C. Kuhakarn. CHAPTER 6: Hydroxylation, Epoxidation and Related Reactions 6.1: Proline-Catalysed a-Aminoxylation of Aldehydes and Ketones Y. Hayashi and M. Shoji. 6.2: Ru/ Silica* Cat* TEMPO(c)-Mediated Oxidation of Alkenes to a-Hydroxyacids R. Ciriminna and M. Pagliaro. 6.3: Catalytic Enantioselective Epoxidation of trans-Disubstituted and Trisubstituted Alkenes with Arabinose-Derived Ulose T.K. M. Shing, G.Y.C. Leung and T. Luk. 6.4: VO(acac)2/ TBHP-Catalysed Epoxidation of 2-(2-Alkenyl)phenols. Highly Regio- and Diastereo-selective Oxidative Cyclisation to 2,3-Dihydrobenzofuranols and 3-Chromanols A. Lattanzi and A. Scettri. 6.5: An Oxalolidinone Ketone Catalyst for the Asymmetric Epoxidation of cis-Olefins D. Goeddel and Y. Shi. 6.6: a-Fluorotropinone Immobilised on Silica: a New Stereoselective Heterogeneous Catalyst for Epoxidation of Alkenes with Oxone G. Sartori, A. Armstrong, R. Maggi, A. Mazzacani, R. Sartorio, F. Bigi and B. Dominguez-Fernandez. 6.7: Asymmetric Epoxidation Catalysed by Novel Azacrown Ether-Type Chiral Quaternary Ammonium Salts under Phase-Transfer Catalytic Conditions K. Hori, K. Tani, and Y. Tohda. 6.8: Enantioselective Epoxidation of Olefins using Phase-Transfer Conditions and [6-N-((S)-1,2,2-Trimethylpropyl)-5H-dibenz[c,e]azepinium] [rac-TRISPHAT] Salt as Catalyst J. Vachon, C. Perollier, A. Martinez and J. Lacour. 6.9: Catalytic Asymmetric Epoxidation of a,Unsaturated Esters Promoted by a Yttrium-Biphenyldiol Complex M. Shibasaki, H. Kakei and S. Matsunaga.. 6.10: Catalytic Enantioselective Epoxidation of a, -Enones with a BINOL-Zinc Complex A. Minatti and K.H. Dotz 6.11: Asymmetric Epoxidation of Phenyl 2-(3'-Pyridylvinyl) Sulfone using Polyleucine/ Hydrogen Peroxide Gel M. Pitts and J. Whittall. CHAPTER 7: Oxidation of Ketones to Lactones or Enones 7.1: Synthesis of 2-(Phosphinophenyl)pyridine Ligand and its Application to Palladium-Catalysed Asymmetric Baeyer- Villiger Oxidation of Prochiral Cyclobutanones K. Ito and T. Katsuki. 7.2: (D)-Codeinone from (D)-Dihydrocodeinone via the Use of Modified o-Iodoxybenzoic Acid (IBX) P. Mather and J. Whittall. CHAPTER 8: Oxidative C-C Coupling 8.1: Enantioselective Oxidative Coupling of 2-Naphthols Catalysed by a Novel Chiral Vanadium Complex N-S. Xie, Q-Z. Liu, Z-B. Luo, L-Z. Gong, A-Q. Mi and Y-Z. Jiang. 8.2: Catalytic Oxidative Cross-Coupling Reaction of 2-Naphthol Derivatives S. Habaue and T. Temma. 8.3: Oxidative Coupling of Benzene with a,-Unsaturated Aldehydes by Pd(OAc)2/ HPMoV/ O2 System T. Yamada, S. Sakaguchi and Y. Ishii. CHAPTER 9: Oxidation of Sulfides and Sulfoxides 9.1: The First Example of Direct Oxidation of Sulfides to Sulfones by an Osmate- Molecular Oxygen System B.M. Choudary, C. Reddy, V. Reddy, B.V. Prakash, M.L. Kantam and B. Sreedhar. 9.2: Selective Oxidation of Sulfides to Sulfoxides and Sulfones using Hydrogen Peroxide (H2O2) in the Presence of Zirconium Tetrachloride K. Bahrami. 9.3: WO3-30% H2O2-Cinchona Alkaloids: a New Heterogeneous Catalytic System for Asymmetric Oxidation and Kinetic Resolution of Racemic Sulfoxides V. V. Thakur and A. Sudalai. 9.4: Benzyl-4,6-isopropylidene-a-(D)-glucopyranoside, 2-deoxy-2-[[(2-hydroxy-3,5-di-tert-butylphenyl)methylene]amine] as a Ligand for Vanadium-Catalysed Asymmetric Oxidation of Sulfides R. Del Litto, G. Roviello and F. Ruffo. 9.5: Asymmetric Sulfoxidation of Aryl Methyl Sulfides with H2O2 in Water A. Scarso and G. Strukul

Read more less

Book SynopsisBringing together current advances and in-depth reviews of bio-based industrial products and agricultural biotechnology, Biocatalysis and Molecular Engineering examines the recent energy and food crises and points out the importance of using bio-based products from renewable resources and agricultural biotechnology.Table of ContentsPreface. Contributors. Section I. Improvement of Agronomic and Microbial Traits. 1.Insights into the Structure and Function of Acyl-CoA: Diacylglycerol Acyltransferase (Rodrigo M.P. Siloto, Qin Liu, Randall J. Weselake, Xiaohua He, and Thomas McKeon). 2. Improving Enzyme Character by Molecular Breeding: Preparation of Chimeric Genes (Kiyoshi Hayashi, Motomitsu Kitaoka, and Mamoru Nishimoto). 3. Production and Accumulation of Unusual Fatty Acids in Plant Tissues (D. Hildebrand, J.R, Thoguru, S. Rao, R Li, and T. Hatanaka). 4. Preparation of Oleaginous Yeast by Genetic Modification and Its Potential Applications (Yasushi Kamisaka). 5. Improving Value of Oil Palm Using Genetic Engineering (Ghulam Kadir Admad Parveez, Abrizah Othman, Umi Salamah Ramli, Ravigadevi Sambanthamurthi, Abdul Masani Mat Yunus, Ahmad Tarmizi Hashim, Ahmad Kushairi Din, and Mohd Basri Wahid). 6. Potential in Using Arabidopsis Acyl-Coenzyme-A-Binding Proteins in Engineering Stress-Tolerant Plants (Mee-Len Chye, Shi Xiao, Qin-Fang Chen, and Wei Gao). 7. Modification of Lipid Composition by Genetic Engineering in Oleaginous Marine Microorganism, Thraustochytrid (Tsunehiro Aki, Hiroaki Iwasaka, Hirofumi Adachi, Maya Nanko, Hiroko Kawasaki, Seiji Kawamoto, Toshihide Kakizono, and Kazuhisa Ono). 8. Integrated Approaches to Manage Tomato Yellow Leaf Curl Viruses (R. C, de la Peña, P. Kadirvel, S. Venkatesan, L. Kenyon, and J. Hughes). 9. Carbohydrate Acquisition During Legume Seed Development (Jocelyn A. Ozga, Dennis M. Reinecke, and Pankaj K. Bhowmik). 10. Biotechnology Enhancement of Phytosterol Biosynthesis in Seed Oils (Qilin Chen and Jitao Zou). Section II: Functional Foods and Biofuels. 11. Dietary Phosphatidylinositol in Metabolic Syndrome (Bungo Shirouchi, Koji Nagao, and Teruyoshi Yanagita). 12. Biotechnological Enrichment of Cereals with Polyunsaturated Fatty Acids (Milan Certik, Zuzana Adamechova, and Lucia Slavikova). 13. Lipophilic Ginsenoside Derivatives Production (Jiang-Ning Hu and Ki-Teak Lee). 14. Brown Seaweed Lipids as Possible Source for Nutraceuticals and Functonal Foods (M. Airanthi K. Widjaja-Adhi, Takayuki Tsukui, Masashi Hosokawa, and Kazuo Miysahita). 15. Processes for Production of Biodiesel Fuel (Yomi Watanabe and Yuji Shimada). 16. Noncatalytic Alcoholysis Process for Production of Biodiesel Fuel: Its Potential in Japan and Southeast Asia (Hiroshi Nabetani, Shoji Hagiwara, and Mitsutoshi Nakajima). 17. Use of Coniochaeta ligniaria to Detoxify Fermentation Inhibitors Present in Cellulosic Sugar Streams (Nancy N. Nichols, Bruce S. Dien, Maria J. López, and Joaquín Moreno). 18. Omics Applications to Biofuel Research (Tzi-Yuan Wang, Hsin-Liang Chen, Wen-Hsiung Li, Huang-Mo Sung, and Ming-Che Shih). Section III: Renewable Bioproducts. 19. Biotechnological Uses of Phospholipids (Jeong Jun Han, Jae Kwang Song, Joon Shick Rhee, and Suk Hoo Yoon). 20. Application of Partition Chromatographic Theory on the Routine Analysis of Lipid Molecular Species (Koretaro Takahashi and Tsugihiko Hirano). 21. Dehydrogenase-Catalyzed Synthesis of Chiral Intermediates for Drugs (Ramesh N. Patel). 22. Engineering of Bacterial Cycochrome P450 Monooxygenase as Biocatalysts for Chemical Synthesis and Environmental Bioremedication (Jun Ogawa, Quin-Shan Li, Sakayu Shimizu, Vlada Urlancher, and Rolf D. Schmid). 23. Glycosynthases from Inverting Hydrolases (Motomitsu Kitaoka). 24. Molecular Species of Diacylglycerols and Triacylglycerols Containing Dihydroxy Fatty Acids in Castor Oil (Jiann-Tsyh Lin). 25. Biocatalytic Production of Lactobionic Acid (Hirofumi Nakano, Takaaki Kiryu, Taro Kiso, and Hiromi Murakami). 26. Recent Advances in Aldolase-Catalyzed Synthesis of Unnatural Sugars and Iminocyclitols (Masakazu Sugiyama, Zhangyong Hong, William A. Greenberg, and Chi-Huey Wong). 27, Production of Value-Added Products by Lactic Acid Bacteria (Siqing Liu, Kenneth M. Bischoff, Yebo Li, Fengjie Cui, Hassan Azaizeh, and Ahmed Tafesh). 28. Enzymatic Synthesis of Glycosides Using Alpha-Amylase Family Enzymes (Kazuhisa Sugimoto, Takahisa Nishimura, Koji Nomura, Hiromi Nishiura, and Takashi Kuriki). 29. Biological Synthesis of Gold and Silver Nanoparticles Using Plant Leaf Extracts and Antimicrobial Application (Beom Soo Kim and Jae Yong Song). 30. Potential Approach of Microbial Conversion to Develop New Antifungal Products of Omega-3 Fatty Acids (Vivek K. Bajpai, Sun-Chul Kang, Hak-Ryul Kim, and Ching T. Hou). Index.

Read more less

Book SynopsisHomogeneous catalysis by soluble metal complexes has gained considerable attention due to its unique applications and features such as high activity and selectivity. Catalysis of this type has demonstrated impressive achievements in synthetic organic chemistry and commercial chemical technology. Homogeneous Catalysis with Metal Complexes: Kinetic Aspects and Mechanisms presents a comprehensive summary of the results obtained over the last sixty years in the field of the kinetics and mechanisms of organic and inorganic reactions catalyzed with metal complexes. Topics covered include: Specific features of catalytic reaction kinetics in the presence of various mono- and polynuclear metal complexes and nanoclusters Multi-route mechanisms and the methods of their identification, as well as approaches to the kinetics of polyfunctional catalytic systems Principles and features of the dynamic behavior of nonlinear kinetic models The potTable of ContentsNotations and Abbreviations xi Preface to English Edition xvii Preface xix Acknowledgments xxi About the Author xxiii Introduction 1 1 State-of-the-Art in the Theory of Kinetics of Complex Reactions 21 1.1 Main concepts of the Horiuti–Temkin theory of steady-state reactions 21 1.1.1 Reaction mechanism: Stoichiometry and routes 22 1.1.2 Kinetics: Reaction rates with respect to substances and over routes 32 1.1.3 Kinetic polynomial 42 1.1.4 Determining the number of independent parameters in a kinetic model. The problem of identifiability of parameters 44 1.2 Quasi-steady-state and quasi-equilibrium approximations in chemical kinetics 47 1.2.1 Theoretical criteria of quasi-steady-state intermediate concentrations and quasi-equilibrium steps 49 1.2.2 Experimental criteria of applicability of quasi-steady-state approximation in various systems 60 1.3 Methods of graph theory in chemical kinetics and in theory of complex reaction mechanisms 62 1.3.1 Linear mechanisms 62 1.3.2 Nonlinear mechanisms 71 1.3.3 Other fields of application of kinetic and bipartite graphs in chemical kinetics and in theory of complex reaction mechanisms 76 1.4 Elementary steps – Selection rules 79 1.4.1 Main postulates, laws, and principles 79 1.4.2 Energy selection rules for elementary steps 88 1.4.3 Quantum-chemical selection rules for elementary steps 92 1.4.4 Topological selection rules for elementary steps 108 References 113 2 Complexity Functions of Catalysts and Reactants in Reactions Involving Metal Complexes 121 2.1 Mononuclear metal complexes 122 2.1.1 Complexity functions: variants I and II 134 2.1.2 Complexity functions: variants III and IV 149 2.1.3 General problems and recommendations 165 2.2 Polynuclear complexes in homogeneous catalytic and noncatalytic reactions 167 2.2.1 Systems with formation of associates 168 2.2.2 Systems with mononuclear and polynuclear complexes of various types 182 2.3 Catalysis with polynuclear copper(I) halide complexes in superconcentrated solutions 193 2.3.1 Copper(I) chloride complexes in solution and in crystalline state 194 2.3.2 Kinetics of catalytic reactions of alkynes in concentrated NH4Cl–CuCl aqueous solutions at constant complexity functions FCu and FCl 203 2.3.3 Determination of compositions of catalytically active copper(I) complexes in various reactions 210 2.3.4 Studying π and σ complexes of copper(I) with alkynes in crystalline state and in solution 216 2.3.5 Mechanisms of acetylene dimerization and hydrocyanation reactions. Crystallochemical aspects 227 References 231 3 Multi-Route Mechanisms in Reactions Involving Metal Complexes 239 3.1 Factors accounting for the appearance and kinetic features of multi-route mechanisms 239 3.2 Analysis of multi-route reaction kinetics 246 3.3 Conjugation nodes and artificial multi-route character 271 3.4 Conjugate processes 304 3.4.1 Classical approach 305 3.4.2 Kinetic and thermodynamic conjugation in consecutive reactions 309 3.4.3 Conjugation in chain reactions 317 3.4.4 Conclusions 323 References 328 4 Polyfunctional Catalytic Systems 335 4.1 Oxidation reactions of organic and inorganic compounds 341 4.1.1 Oxidation of alkenes 341 4.1.2 Oxidation of 1,3-dienes 356 4.1.3 Oxidation of alkynes and arenes 366 4.1.4 Oxidation of inorganic compounds 369 4.2 Reactions of chlorination and oxidative chlorination of organic compounds 372 4.2.1 Oxidative chlorination of alkynes 372 4.2.2 Oxidative chlorination of 1,3-dienes 384 4.2.3 Polyfunctional catalytic systems in chlorination reactions 386 4.3 Oxidative carbonylation of organic compounds 389 4.3.1 Oxidative carbonylation of HY molecules (Y = OR, OPh, NR2, Ar, Alk) 390 4.3.2 Oxidative carbonylation of alkenes, dienes, and alkynes 400 4.4 Additive carbonylation of alkynes, alkenes, dienes, and alcohols 408 4.5 Substitution and addition reactions in alkyne chemistry 412 4.6 General problems in PFCS theory and practice 423 4.6.1 PFCSs and principles of their functioning 423 4.6.2 Kinetic and chemical functions of p-benzoquinone and other quinones in PFCSs 426 4.6.3 Variants of association of catalytic reactions and catalytic systems 436 References 442 5 Mechanisms of Formation of Catalytically Active Metal Complexes 453 5.1 Main stages of catalytic process 454 5.2 Chemical reactions involved in the formation of active centers 457 5.3 Mechanisms of active center formation in particular processes 468 5.3.1 Mechanisms of active metal complex formation in PdBr2 –LiBr–P(OPh)3–HBr–n-C4H9OH catalytic system for acrylate synthesis 468 5.3.2 Carbene metal complexes in metathesis of olefins and analogous processes 471 5.3.3 Mechanisms of 1-butene isomerization in Ni[P(OEt)3]4–H2SO4 –MeOH system 488 5.3.4 Features of the formation and decay of active centers in acrylic derivatives synthesis by the Reppe Method 490 5.3.5 Protecting active centers by catalytic process from destruction 492 5.3.6 Mechanism of active center formation in Pd(OAc)2 –PPh3 –p-benzoquinone–MeOH catalytic system for alkyne oxidative carbonylation at ≡C–H bond 494 5.3.7 Catalysis with small palladium(I) halide and carbonyl halide clusters 499 5.3.8 Mechanisms of formation of large cluster complexes and microheterogeneous nanoparticles 507 5.3.9 Synthesis and characterization of giant palladium clusters 512 5.3.10 Approaches to identification of the nature of catalytically active species in solutions of metal complexes 513 5.4 Examples of chain mechanisms and chain carriers of various natures 518 5.5 Classification of mechanisms of real catalytic processes 528 References 536 6 Nonlinear Effects (Critical Phenomena) in Reaction Dynamics in Homogeneous Catalysis with Metal Complexes 545 6.1 Historical notes 548 6.2 Physicochemical factors responsible for the critical phenomena in homogeneous reactions 551 6.2.1 Thermodynamic features of nonequilibrium processes near and far from equilibrium 552 6.2.2 Dynamic behavior of systems with linear mechanisms in open reactors with complete mixing 565 6.2.3 Nonlinearity of kinetic models 570 6.2.4 Main principles and methods of analysis of the dynamic behavior of nonlinear systems 573 6.3 Analysis of simple nonlinear kinetic models 582 6.4 Mechanisms of oscillatory catalytic reactions 630 6.4.1 Belousov–Zhabotinskii reaction (BZ reaction) 630 6.4.2 Liquid-phase oxidation of organic compounds by oxygen in Co(OAc)2–Br–CH3COOH system 640 6.4.3 Oxidative carbonylation of alkynes in solutions of palladium complexes 644 References 658 7 Rational Strategy for Designing Kinetic Models and Studying Complex Reaction Mechanisms 665 7.1 Stages in the development of chemical kinetics and methodological aspects of the strategy of studying complex reaction mechanisms 666 7.2 Alternative strategies for studying complex reaction mechanisms and designing kinetic models 669 7.2.1 Traditional strategy 669 7.2.2 Rational strategy 671 7.3 Hypothesis generation methods and examples 674 7.4 Hypothesis generation programs: Application examples and related problems 677 7.4.1 Combinatorics on kinetic graphs 677 7.4.2 ChemComb (Comb 1) program 686 7.4.3 MECHEM program 691 7.4.4 NetGen program 694 7.4.5 TAMREAC program 697 7.4.6 ChemNet program 697 7.4.7 Large reaction networks and problems in discrimination of hypotheses and construction of compact kinetic models 713 References 733 8 Effect of Medium on Reaction Rates in Homogeneous Catalysis with Metal Complexes 741 8.1 Effect of electrolytes on the activity coefficients of reaction medium components 743 8.2 Effect of electrolytes on the solubility of nonelectrolytes (gases and organic compounds) 748 8.3 Effect of electrolytes on the rates of elementary reactions between ions and uncharged substrates 752 8.4 Kinetics of catalytic reactions in concentrated aqueous electrolyte (HCl) solutions 754 8.5 Organic solvents in homogeneous catalysis with metal complexes 760 8.5.1 Main physical and chemical properties of solvents 760 8.5.2 Association of solvents and formation of molecular complexes 763 8.5.3 Metal complexes in organic and aqueous-organic solvents 765 8.5.4 Ion association, ion pairs, and specific salt effect in organic solvents 771 8.6 Strong protonic acids in organic solvents and kinetics of catalytic reactions with metal complexes in these media 775 8.6.1 Structure and properties of strong acid solutions in organic solvents 776 8.6.2 Kinetics of catalytic reactions in HCl–NMP, HCl–C2H5OH, and HCl–C2H5OH–CH3CN systems 783 8.7 Ionic liquids in catalytic chemistry 787 References 791 Conclusion 797 Subject Index 801 Index of Metals 803 Index of Reactions 805

Read more less

Book SynopsisIn this exciting new title all aspects of nanoalloys are explored, including synthesis, characterisation, theory and simulation, property measurements and technological applications. Nanoalloys are of great interest due to their unique structures and properties which are distinct from those of the pure elemental clusters. They are used in a wide range of applications and their chemical and physical properties can be tuned by varying composition, atomic ordering, or clusters. This book will be of interest to academics working at the interfaces between chemistry, materials, physics and nanoscience, and to those working in the nanotechnology, catalysis and optoelectronics areas of industry.Table of ContentsNanoalloys: tuning properties and characteristics through size and composition A study of bimetallic Cu-Ag, Au-Ag and Pd-Ag clusters adsorbed on a double-vacancy-defected MgO(100) terrace Global optimisation and growth simulation of AuCu clusters Mechanical properties of bimetallic crystalline and nanostructured nanowires Solid-solution precursor to melting in onion-ring Pd-Pt nanoclusters: a case of second-order-like phase change? Atomistic computer simulations on the generation of bimetallic nanoparticles Dynamical equilibrium in nanoalloys

Read more less

Book SynopsisOver the last decade, the area of homogeneous catalysis with transition metal has grown in great scientific interest and technological promise, with research in this area earning three Nobel Prizes and filing thousands of patents relating to metallocene and non-metallocene single site catalysts, asymmetric catalysis, carbon-carbon bond forming metathesis and cross coupling reactions. This text explains these new developments in a unified, cogent, and comprehensible manner while also detailing earlier discoveries and the fundamentals of homogeneous catalysis. Serving as a self-study guide for students and all chemists seeking to gain entry into this field, it can also be used by experienced researchers from both academia and industry for referring to leading state of the art review articles and patents, and also as a quick self-study manual in an area that is outside their immediate expertise. The book features: Topics including renewable feed stocks (biofuel, glycerol), carTable of Contents1. Chemical Industry and Homogeneous Catalysis1.1 Feed Stocks, Fuels and Catalysts1.2 Crude Oil to Gasoline and Basic Building Blocks by Heterogeneous catalysts1.3 Basic Building Blocks to Downstream Products by Homogeneous Catalysis1.4 Comparison among Different Types of Catalysis1.5 Catalyst Recovery1.6 Environmental IssuesProblemsBibliography2. Basic Chemical Concepts2.1 Ligands2.2 Metals2.3 Important Reaction TypesProblemsBibliography3. Methods of Investigation3.1 Catalytic cycle and intermediates3.2 Spectroscopic Studies3.3 Kinetic Studies3.4 Model Compounds3.5 Computational Techniques (Theoretical Calculation)3.6 Asymmetric CatalysisProblemsBibliography4. Carbonylation and Related Reactions4.1 Introduction4.2 Carbonylation and Manufacture of Acetic Acid4.3 Carbonylation of Other Alcohols4.4 Carbonylation of Methyl Acetate4.5 Carbonylation of Alkynes4.6 Other carbonylation and hydrocarboxylation reactions4.7 C1-Chemistry4.8 Engineering AspectsProblemsBibliography5. Hydrogenation and Other Hydrogen Based Catalytic Reactions5.1 Hydrogenation5.2 Hydroformylation5.3 Other Hydroformylation reactions5.4 Asymmetric Hydroformylation5.5 Hydrosilylation5.6 Hydrocyanation5.7 HydroaminationProblemsBibliography6. Polymerization and Selective Oligomerization of Alkenes6.1 Introduction6.2 Early Catalysts for Polyethylene and Polypropylene6.3 Modern Ziegler-Natta Catalyst6.4 Mechanistic Studies6.5 Single Site Catalysts6.6 Ethylene Polymerization with Polar comonomers6.7 Polymers of Other Alkenes6.8 Oligomerization of Ethylene6.9 Engineering AspectsProblemsBibliography7. Selective C-C Bond Forming Reactions With Alkenes7.1 Introduction7.2 Di-, Tri-, Tetramerization and Codimerization reactions7.3 Metathesis Reactions7.4 Pd-Catalyzed Cross Coupling Reactions7.5 Metal catalyzed Cyclopropanation and CycloadditionProblemsBibliography8. Oxidation8.1 Introduction8.2 Wacker Oxidation8.3 Metal-Catalyzed Liquid-Phase Autoxidation8.4 Polymers from Autoxidation Products8.5 Selective Oxidations8.6 Engineering and Safety ConsiderationsProblemsBibliography

Read more less

Book SynopsisOpens the door to the sustainable production of pharmaceuticals and fine chemicals Driven by both public demand and government regulations, pharmaceutical and fine chemical manufacturers are increasingly seeking to replace stoichiometric reagents used in synthetic transformations with catalytic routes in order to develop greener, safer, and more cost-effective chemical processes. This book supports the discovery, development, and implementation of new catalytic methodologies on a process scale, opening the door to the sustainable production of pharmaceuticals and fine chemicals. Pairing contributions from leading academic and industrial researchers, Sustainable Catalysis focuses on key areas that are particularly important for the fine chemical and pharmaceutical industries, including chemo-, bio-, and organo-catalytic approaches to C?H, C?N, and C?C bond-forming reactions. Chapters include academic overviews of current innovations and industrial case stuTrade Review“In brief, I have read this book with pleasure and I recommend it to all chemists working or getting started in the field of catalysis.” (Angew. Chem. Int. Ed., 1 October 2014) Table of ContentsForeword vii Preface ix Contributors xi Abbreviations xiii 1 Catalytic Reduction of Amides Avoiding LiAlH4 or B2H6 1 Deborah L. Dodds and David J. Cole-Hamilton 2 Hydrogenation of Esters 37 Lionel A. Saudan 3 Synthesis of Chiral Amines Using Transaminases 63 Nicholas J. Turner and Matthew D. Truppo 4 Development of a Sitagliptin Transaminase 75 Jacob M. Janey 5 Direct Amide Formation Avoiding Poor Atom Economy Reagents 89 Benjamin M. Monks and Andrew Whiting 6 Industrial Applications of Boric Acid and Boronic Acid-Catalyzed Direct Amidation Reactions 111 Joanne E. Anderson, Jannine Cobb, Roman Davis, Peter J. Dunn, Russ N. Fitzgerald, and Alan J. Pettman 7 OH Activation for Nucleophilic Substitution 121 Jonathan M.J. Williams 8 Application of a Redox-Neutral Alcohol Amination in the Kilogram-Scale Synthesis of a GlyT1 Inhibitor 139 Martin A. Berliner 9 Olefin Metathesis: From Academic Concepts to Commercial Catalysts 163 Justyna Czaban, Christian Torborg, and Karol Grela 10 Challenge and Opportunity in Scaling-up Metathesis Reaction: Synthesis of Ciluprevir (BILN 2061) 215 Nathan Yee, Xudong Wei, and Chris Senanayake 11 C–H Activation of Heteroaromatics 233 Koji Hirano and Masahiro Miura 12 The Discovery of a New Pd/Cu Catalytic System for C–H Arylation and Its Applications in a Pharmaceutical Process 269 Jinkun Huang, Xiang Wang, and Johann Chan 13 Diarylprolinol Silyl Ethers: Development and Application as Organocatalysts 287 Hiroaki Gotoh and Yujiro Hayashi 14 Organocatalysis for Asymmetric Synthesis: From Lab to Factory 317 Feng Xu 15 Catalytic Variants of Phosphine Oxide-Mediated Organic Transformations 339 Stephen P. Marsden 16 Formation of C–C Bonds Via Catalytic Hydrogenation and Transfer Hydrogenation 363 Joseph Moran and Michael J. Krische Index 409

Read more less

Book SynopsisServing as a user''s manual for synthetic organic and catalytic chemists, this book guides chemists in the design and choice of ligands to catalyze organic reactions and apply the results for more efficient, green, and practical synthesis. Focuses on the role of ligands in metal complexes that catalyze green organic transformations: a hot topic in the area of organic synthesis and green chemistry Offers a comprehensive resource to help readers design and choose ligands and understand selectivity/reactivity characteristics Addresses a gap by taking novel ligand approaches and including up-to-date discussion on hydrogen transfers and reactions Presents important industrial perspective and provides rational explanations of ligand effects, impacts, and noveltyTable of ContentsPreface ix Abbreviation xi Part I N-Heterocyclic Carbene Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 1 1 Oxidation and Hydrogenation Reactions Catalyzed by Transition Metal Complexes Bearing N-Heterocyclic Carbene Ligands 3 1.1 Introduction, 3 1.2 Oxidation of Alcohols Based on Hydrogen Transfer, 3 1.3 Oxidation of Alcohols Based on Dehydrogenation, 10 1.4 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds, 12 1.5 Other Related Hydrogenative Reactions, 21 References, 25 2 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing N-Heterocyclic Carbene Ligands 27 2.1 Introduction, 27 2.2 Carbon–Carbon Bond Formation Based on Hydrogen Transfer, 27 2.3 Carbon–Nitrogen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 37 2.4 Carbon–Oxygen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 46 References, 52 Part ii η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 55 3 Oxidation and Hydrogenation Catalyzed by Transition Metal Complexes Bearing η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands 57 3.1 Introduction, 57 3.2 Oxidation of Alcohol Based on Hydrogen Transfer and Dehydrogenation, 59 3.3 Oxidation of Amine Based on Hydrogen Transfer, 68 3.4 Hydrogenation and Transfer Hydrogenation of Carbonyl Compounds, 71 3.5 Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds, 79 References, 84 4 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands 87 4.1 Introduction, 87 4.2 Carbon–Nitrogen Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 88 4.3 Carbon–Oxygen Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 97 4.4 Carbon–Carbon Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 102 References, 105 Part iii Pincer Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 107 5 Dehydrogenation of Alkanes Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 109 5.1 Introduction, 109 5.2 Conversion of Alkanes into Alkenes Based on Hydrogen Transfer, 109 5.3 Dehydroaromatization of Alkanes Based on Hydrogen Transfer, 115 5.4 Alkane Metathesis by Tandem Alkane Dehydrogenation and Alkene Metathesis, 118 5.5 Conversion of Alkanes into Alkenes Based on Dehydrogenation, 121 References, 126 6 Oxidation and Hydrogenation Reactions Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 128 6.1 Introduction, 128 6.2 Oxidation of Alcohols Based on Hydrogen Transfer and Dehydrogenation, 128 6.3 Dehydrogenation of Amines, 137 6.4 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds, 141 References, 157 7 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 159 7.1 Introduction, 159 7.2 Carbon–Carbon Bond Formation Based on Hydrogen Transfer, 159 7.3 Carbon–Nitrogen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 161 7.4 Carbon–Oxygen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 173 References, 182 Part iv Bidentate and Miscellaneous Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 183 8 Oxidation and Dehydrogenation of Alcohols and Amines Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 185 8.1 Introduction, 185 8.2 Oxidation of Alcohols Based on Hydrogen Transfer with Oxidant, 185 8.3 Dehydrogenative Oxidation of Alcohols without Oxidant, 209 8.4 Oxidation of Amines Based on Hydrogen Transfer and Dehydrogenation, 220 References, 224 9 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 228 9.1 Introduction, 228 9.2 Hydrogenation and Transfer Hydrogenation of Carbonyl and Related Compounds, 229 9.3 Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds, 263 References, 274 10 Bond-Forming Reactions Based on Hydrogen Transfer Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 278 10.1 Introduction, 278 10.2 Carbon–Carbon Bond-Forming Reactions Based on Hydrogen Transfer, 279 10.3 Carbon–Nitrogen Bond-Forming Reactions Based on Hydrogen Transfer, 296 10.4 Carbon–Oxygen Bond-Forming Reactions Based on Hydrogen Transfer, 321 References, 330 Index 335

Read more less

Book SynopsisPhotocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most important catalysts discovered today based on first and second row transition metals. A strong emphasis is placed on the description of their performance, as well as how they work from a mechanistic perspective. In addition, a theoretical description of some of the most relevant catalysts based on DFT are presented, as well as a description of related natural systems, such as the oxygen evoTable of ContentsList of Contributors xi Preface xv 1. Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis 1 Ivan Rivalta, Gary W. Brudvig, and Victor S. Batista 1.1 Introduction 1 1.2 Structural Studies of the OEC 2 1.3 The Dark-Stable State of the OEC 4 1.4 Biomimetic Oxomanganese Complexes 6 1.5 Base-Assisted O–O Bond Formation 7 1.6 Biomimetic Mn Catalysts for Artificial Photosynthesis 8 1.7 Conclusion 11 Acknowledgments 12 References 12 2. O–O Bond Formation by a Heme Protein: The Unexpected Efficiency of Chlorite Dismutase 15 Jennifer L. DuBois 2.1 Introduction 15 2.2 Origins of O2-Evolving Chlorite Dismutases (Clds) 15 2.3 Major Structural Features of the Proteins and their Active Sites 16 2.4 Efficiency, Specificity, and Stability 20 2.5 Mechanistic Insights from Surrogate Reactions with Peracids and Peroxide 22 2.6 Possible Mechanisms 23 2.7 Conclusion 25 Acknowledgements 25 References 25 3. Ru-Based Water Oxidation Catalysts 29 Laia Francàs, Roger Bofill, Jordi García-Antón, Lluis Escriche, Xavier Sala and Antoni Llobet 3.1 Introduction 29 3.2 Proton-Coupled Electron Transfer (PCET) and Water Oxidation Thermodynamics 31 3.3 O–O Bond Formation Mechanisms 33 3.4 Polynuclear Ru Water Oxidation Catalysts 34 3.5 Mononuclear Ru WOCs 40 3.6 Anchored Molecular Ru WOCs 42 3.7 Light-Induced Ru WOCs 43 3.8 Conclusion 45 Acknowledgments 46 References 46 4. Towards the Visible Light-Driven Water Splitting Device: Ruthenium Water Oxidation Catalysts with Carboxylate-Containing Ligands 51 Lele Duan, Lianpeng Tong, and Licheng Sun 4.1 Introduction 51 4.2 Binuclear Ru Complexes 52 4.3 Mononuclear Ru Complexes 54 4.3.1 Ru–O2N–N3 Analogs 55 4.3.2 Ru–O2N2–N2 Analogs 57 4.4 Homogeneous Light-Driven Water Oxidation 68 4.4.1 The Three-Component System 68 4.4.2 The Supramolecular Assembly Approach 69 4.5 Water Oxidation Device 72 4.5.1 Electrochemical Water Oxidation Anode 72 4.5.2 Photo-Anode for Water Oxidation 74 4.6 Conclusion 75 References 75 5. Water Oxidation by Ruthenium Catalysts with Non-Innocent Ligands 77 Tohru Wada, Koji Tanaka, James T. Muckerman, and Etsuko Fujita 5.1 Introduction 77 5.2 Water Oxidation Catalyzed by Dinuclear Ruthenium Complexes with NILs 81 5.3 Water Oxidation by Intramolecular O–O Coupling with [RuII2 (𝜇-Cl)(bpy)2(btpyan)]3+ 85 5.4 Mononuclear Ru–Aqua Complexes with a Dioxolene Ligand 91 5.4.1 Structural Characterization 91 5.4.2 Theoretical and Electrochemical Characterization 96 5.5 Mechanistic Investigation of Water Oxidation by Dinuclear Ru Complexes with NILs: Characterization of Key Intermediates 101 References 107 6. Recent Advances in the Field of Iridium-Catalyzed Molecular Water Oxidation 113 James A. Woods, Stefan Bernhard, and Martin Albrecht 6.1 Introduction 113 6.2 Bernhard 2008 [11] 114 6.3 Crabtree 2009 115 6.4 Crabtree 2010 116 6.5 Macchioni 2010 117 6.6 Albrecht/Bernhard 2010 117 6.7 Hetterscheid/Reek 2011 118 6.8 Crabtree 2011 119 6.9 Crabtree 2011 120 6.10 Lin 2011 120 6.11 Macchioni 2011 122 6.12 Grotjahn 2011 123 6.13 Fukuzumi 2011 123 6.14 Lin 2012 124 6.15 Crabtree 2012 125 6.16 Albrecht/Bernhard 2012 125 6.17 Crabtree 2012 126 6.18 Beller 2012 127 6.19 Lin 2012 128 6.20 Lloblet and Macchioni 2012 129 6.21 Analysis 130 References 131 7. Complexes of First Row d-Block Metals: Manganese 135 Philipp Kurz 7.1 Background 135 7.2 Oxidation States of Manganese in an Aqueous Environment 137 7.3 Dinuclear Manganese Complexes: Syntheses and Structures 138 7.4 Redox and Acid–Base Chemistry of Mn2-𝜇-WDL Systems 139 7.5 Mn2 Systems: Oxygen Evolution (but not Water Oxidation) Catalysis 142 7.6 Mn2 Complexes/the OEC/Ru2 Catalysts: A Comparison 144 7.7 Heterogeneous Water Oxidation Catalysis by Mn>2 Systems 146 7.8 Conclusion 148 Acknowledgements 148 References 149 8. Molecular Water Oxidation Catalysts from Iron 153 W. Chadwick Ellis, Neal D. McDaniel, and Stefan Bernhard 8.1 Introduction 153 8.2 Fe-Tetrasulfophthalocyanine 154 8.3 Fe-TAML 155 8.4 Fe-mcp 157 8.5 Fe2O3 as a Microheterogeneous Catalyst 158 8.6 Conclusion 160 References 161 9. Water Oxidation by Co-Based Oxides with Molecular Properties 163 Marcel Risch, Katharina Klingan, Ivelina Zaharieva, and Holger Dau 9.1 Introduction 163 9.2 CoCat Formation 164 9.3 Structure and Structure–Function Relations 166 9.4 Functional Characterization 173 9.5 Directly Light-Driven Water Oxidation 175 References 180 10. Developing Molecular Copper Complexes for Water Oxidation 187 Shoshanna M. Barnett, Christopher R. Waidmann, Margaret L. Scheuermann, Jared C. Nesvet, Karen Goldberg and James M. Mayer 10.1 Introduction 187 10.2 A Biomimetic Approach 188 10.2.1 Thermochemistry: Developing Oxidant/Base Combinations as PCET Reagents 189 10.2.2 Copper Complexes with Alkylamine Ligands 190 10.2.3 Copper Complexes with Anionic Ligands 195 10.2.4 Lessons Learned: Thermochemical Insights and Oxidant/Base Compatibility 198 10.3 An Aqueous System: Electrocatalysis with (bpy)Cu(II) Complexes 198 10.3.1 System Selection: bpy + Cu 199 10.3.2 Observing Electrocatalysis 199 10.3.3 Catalyst Turnover Number and Turnover Frequency 201 10.3.4 Catalyst Speciation: Monomer, Dimer, or Nanoparticles? 203 10.4 Conclusion 206 Acknowledgement 206 References 207 11. Polyoxometalate Water Oxidation Catalytic Systems 211 Jordan M. Sumliner, James W. Vickers, Hongjin Lv, Yurii V. Geletii, and Craig L. Hill 11.1 Introduction 211 11.2 Recent POM WOCs 214 11.3 Assessing POM WOC Reactivity 220 11.4 The Ru(bpy)3 2+ ∕S2O8 2-System 221 11.5 Ru(bpy) 3 3+ as an Oxidant for POM WOCs 222 11.6 Additional Aspects of WOC System Stability 224 11.7 Techniques for Assessing POM WOC Stability 224 11.8 Conclusion 227 Acknowledgments 228 References 228 12. Quantum Chemical Characterization of Water Oxidation Catalysts 233 Pere Miró, Mehmed Z. Ertem, Laura Gagliardi, and Christopher J. Cramer 12.1 Introduction 233 12.2 Computational Details 235 12.2.1 Density Functional Theory Calculations 235 12.2.2 Multiconfigurational Calculations 236 12.3 Methodology 237 12.3.1 Solvation and Standard Reduction Potentials 237 12.3.2 Multideterminantal State Energies 238 12.4 Water Oxidation Catalysts 238 12.4.1 Ruthenium-Based Catalysts 238 12.4.2 Cobalt-Based Catalysts 245 12.4.3 Iron-Based Catalysts 248 12.5 Conclusion 251 References 252 Index 257

Read more less

Book SynopsisFour decades of landmark discoveries in heterogeneous catalysis Presenting an historical record of four decades of landmark research, this book draws together an important collection of heterogeneous catalysis papers published by Professor Eli Ruckenstein and his colleagues. One of the most prolific leaders in the field of heterogeneous catalysis today, Dr. Ruckenstein has pioneered methods in catalysis, surface chemistry, and materials science that are now used to develop new chemicals, energy sources, and materials. Heterogeneous Catalysis offers new insights into the underlying mechanisms and chemistry of heterogeneous catalysis. Moreover, the book will help readers develop new applications for both basic research and industry. Coverage includes: Catalysts in various reactions including methane CO2 reforming, methane partial oxidation, and catalytic combustion Applications of materials such as zeolites, meTable of Contents1 Catalytic conversion of methane to synthesis gas by CO2 reforming 1 2 Catalytic conversion of methane to synthesis gas by partial oxidation 79 3 Catalytic combustion of clean as well as nitrogen bound fuels over transitional metal oxides 139 4 Zeolites and their applications as catalysts and/or catalyst supports 223 5 Synthesis of mesoporous V-Mg-O oxides and their applications as catalysts 365 6 Synthesis of polymer supported catalysts and polymer-coated silica supports and their applications in catalysis 404 7 Metal sintering during heating in various atmospheres 473 8 Heterogeneous catalysis – a theoretical approach 667

Read more less

Book SynopsisThis book gradually brings the reader, through illustrations of the most crucial discoveries, into the modern world of chemical catalysis. Readers and experts will better understand the enormous influence that catalysis has given to the development of modern societies. Highlights the field''s onset up to its modern days, covering the life and achievements of luminaries of the catalytic era Appeals to general audience in interpretation and analysis, but preserves the precision and clarity of a scientific approach Fills the gap in publications that cover the history of specific catalytic processesTable of ContentsPreface ix 1 From the Onset to the First Large-Scale Industrial Processes 1 1.1 Origin of the Catalytic Era 1 1.2 Berzelius and the Affinity Theory of Catalysis 4 1.3 Discovery of the Occurrence of Catalytic Processes in Living Systems in the Nineteenth Century 6 1.4 Kinetic Interpretation of Catalytic Processes in Solutions: The Birth of Homogeneous Catalysis 8 1.5 Onset of Heterogeneous Catalysis 18 1.6 First Large-Scale Industrial Processes Based on Heterogeneous Catalysts 26 1.6.1 Sulfuric Acid Synthesis 26 1.6.2 Ammonia Problem 29 1.6.3 Ammonia Oxidation Process 32 1.6.4 Ammonia Synthesis 33 1.7 Fischer–Tropsch Catalytic Process 40 1.8 Methanol Synthesis 44 1.9 Acetylene Production and Utilization 46 1.10 Anthraquinone Process for Hydrogen Peroxide Production 47 References 49 2 Historical Development of Theories of Catalysis 59 2.1 Heterogeneous Catalysis 59 2.2 Chemical Kinetics and the Mechanisms of Catalysis 62 2.3 Electronic Theory of Catalysis: Active Sites 72 References 76 3 Catalytic Processes Associated with Hydrocarbons and the Petroleum Industry 83 3.1 Petroleum and Polymer Eras 83 3.2 Catalytic Cracking, Isomerization, and Alkylation of Petroleum Fractions 84 3.3 Reforming Catalysts 91 3.4 Hydrodesulfurization (HDS) Processes 93 3.5 Hydrocarbon Hydrogenation Reactions with Heterogeneous Catalysts 94 3.6 Olefin Polymerization: Ziegler–Natta, Metallocenes, and Phillips Catalysts 98 3.7 Selective Oxidation Reactions 109 3.7.1 Alkane Oxidation 109 3.7.2 Olefin Oxidation 110 3.7.3 Aromatic Compounds Oxidation 111 3.8 Ammoximation and Oxychlorination of Olefins 113 3.9 Ethylbenzene and Styrene Catalytic Synthesis 117 3.10 Heterogeneous Metathesis 118 3.11 Catalytic Synthesis of Carbon Nanotubes and Graphene from Hydrocarbon Feedstocks 119 References 121 4 Surface Science Methods in the Second Half of the Twentieth Century 131 4.1 Real Dispersed Catalysts versus Single Crystals: A Decreasing Gap 131 4.2 Physical Methods for the Study of Dispersed Systems and Real Catalysts 132 4.3 Surface Science of Single-Crystal Faces and of Well-defined Systems 139 References 147 5 Development of Homogeneous Catalysis and Organocatalysis 155 5.1 Introductory Remarks 155 5.2 Homogeneous Acid and Bases as Catalysts: G. Olah Contribution 156 5.3 Organometallic Catalysts 161 5.4 Asymmetric Epoxidation Catalysts 175 5.5 Olefin Oligomerization Catalysts 179 5.6 Organometallic Metathesis 180 5.7 Cross-Coupling Reactions 186 5.8 Pd(II)-Based Complexes and Oxidation of Methane to Methanol 190 5.9 Non-transition Metal Catalysis, Organocatalysis, and Organo-Organometallic Catalysis Combination 191 5.9.1 Metal-Free Hydrogen Activation and Hydrogenation 192 5.9.2 Amino Catalysis 193 5.10 Bio-inspired Homogeneous Catalysts 194 References 195 6 Material Science and Catalysis Design 205 6.1 Metallic Catalysts 205 6.2 Oxides and Mixed Oxides 208 6.2.1 SiO2 and SiO2-Based Catalysts and Processes 209 6.2.2 Al2O3 and Al2O3-Based Catalysts and Processes 211 6.2.3 SiO2–Al2O3− and SiO2–Al2O3-Based Catalysts and Processes 211 6.2.4 MgO− and MgO-Based Catalysts and Processes 212 6.2.5 ZrO2 and ZrO2-Based Catalysts and Processes 212 6.3 Design of Catalysts with Shape and Transition-State Selectivity 213 6.4 Zeolites and Zeolitic Materials: Historical Details 214 6.5 Zeolites and Zeolitic Materials Structure 218 6.6 Shape-Selective Reactions Catalyzed by Zeolites and Zeolitic Materials 221 6.6.1 Alkanes- and Alkene-Cracking and Isomerization 222 6.6.2 Aromatic Ring Positional Isomerizations 223 6.6.3 Synthesis of Ethyl Benzene, Cumene, and Alkylation of Aromatic Molecules 224 6.6.4 Friedel–Crafts Acylation of Aromatic Molecules 225 6.6.5 Toluene Alkylation with Methanol 225 6.6.6 Asaki Process for Cyclohexanol Synthesis 226 6.6.7 Methanol-to-Olefins (MTO) Process 226 6.6.8 Nitto Process 227 6.6.9 Butylamine Synthesis 227 6.6.10 Beckman Rearrangements on Silicalite Catalyst 227 6.6.11 Partial Oxidation Reactions Using Titanium Silicalite 227 6.6.12 Nylon-6 Synthesis: The Role of Zeolitic Catalysts 229 6.6.13 Pharmaceutical Product Synthesis 229 6.7 Organic–Inorganic Hybrid Zeolitic Materials and Inorganic Microporous Solids 230 6.7.1 Organic–Inorganic Hybrid Zeolitic Materials 230 6.7.2 ETS-10: A Microporous Material Containing Monodimensional TiO2 Chains 231 6.7.3 Hydrotalcites: Microporous Solids with Exchangeable Anions 232 6.8 Microporous Polymers and Metal–Organic Frameworks (MOFs) 232 6.8.1 Microporous Polymers 232 6.8.2 Metal–organic Frameworks 234 References 235 7 Photocatalysis 243 7.1 Photochemistry and Photocatalysis: Interwoven Branches of Science 243 7.2 Photochemistry Onset 245 7.3 Physical Methods in Photochemistry 249 7.4 Heterogeneous and Homogeneous Photocatalysis 251 7.5 Natural Photosynthesis as Model of Photocatalysis 253 7.6 Water Splitting, CO2 Reduction, and Pollutant Degradation: The Most Investigated Artificial Photocatalytic Processes 256 7.6.1 Water Splitting 257 7.6.2 CO2 Photoreduction 261 7.6.3 Photocatalysis in Environmental Protection 263 References 264 8 Enzymatic Catalysis 269 8.1 Early History of Enzymes 269 8.2 Proteins and Their Role in Enzymatic Catalysis 273 8.3 Enzymes/Coenzymes Structure and Catalytic Activity 284 8.4 Mechanism of Enzyme Catalysis 288 8.5 Biocatalysis 294 References 295 9 Miscellanea 299 9.1 Heterogeneous and Homogeneous Catalysis in Prebiotic Chemistry 299 9.2 Opportunities for Catalysis in the Twenty-First Century and the Green Chemistry 312 References 317 Index 321

Read more less

Book SynopsisThe development of new asymmetric catalytic methods is of fundamental importance to industrial synthetic chemistry. The demand for optically pure synthetic intermediates and the drive to adopt greener methods of synthesis have stimulated a growing interest in biocatalysis as a selective and environmentally benign synthetic technique. Practical Biotransformations: A Beginner''s Guide provides an introduction to microbes and enzymes and demonstrates their practical applications in synthetic organic chemistry. Designed as a laboratory manual, this user-friendly guide discusses standard laboratory techniques, with appropriate advice on aspects of microbial practice and associated safety. Topics covered include: An introduction to equipment in a biotransformations laboratory An overview of biocatalyst sources Maintenance and growth of biocatalysts Example biotransformations using commerciaTrade Review?The book provides a good overview and appropriately conceived outline of this complex topic, enabling the interested reader to begin work with enzymes quickly and without unnecessary complications.? (Angewandte Chemie, October 2009) ?Gogan presents a beginner's guide to microbes and enzymes and how to use them for synthetic organic reactions in the laboratory.? ( Book News, September 2009) ?This book is easy to read and well organized and can be dipped in and out of, depending on your level of experience in different areas. ? Overall and excellent, interesting and user-friendly manual/textbook.? (Chemistry World, August 2009) Table of ContentsChapter 1: Biotransformations, Microbes and Enzymes. 1.1 Introduction. 1.2 Biotransformations. 1.3 Microorganisms. 1.4 Organism nomenclature. 1.5 Enzymes. 1.6 Types of Enzymatic reactions. 1.7 Enzymatic Cofactors. 1.8 Some Basic Characteristics of Enzyme Catalysis. 1.9 Types of Biocatalyst - Biotransformations by ‘whole cells’ or isolated enzymes. 1.10. Conclusion. Chapter 2: An overview of biocatalyst sources and web-based information. 2.1 Introduction. 2.2 Microbial culture collections. 2.3 Obtaining organisms from other research groups. 2.4 Selective Enrichments. 2.5 Metagenomics. 2.6 Enzyme Suppliers and Biocatalyst Development Companies. 2.7 Genome mining for biocatalysts. 2.8 Obtaining amino acid and gene sequence information on biocatalysts. 2.9 Obtaining DNA templates for cloning. 2.10 Custom Gene Synthesis. 2.11 Other interesting web resources for biocatalysis. 2.12 Conclusion. Chapter 3: Setting up a laboratory for biotransformations. 3.1 Introduction. 3.2 Microbiological Containment. 3.3 On containment issues and genetically-modified organisms. 3.4 Equipment for handling microorganisms. 3.5 Techniques and terms in microbiology - Sterility, Asepsis and Aseptic Technique. 3.6 Disposal of viable microbial waste and disinfection of reusable equipment. 3.7 Equipment for enzymology and molecular biology. 3.8 General reagents and chemicals in a Biotransformations Laboratory. 3.9 Conclusion. Chapter 4: A beginner’s guide to preparative whole-cell microbial biotransformations. 4.1 Introduction. 4.2 Storage, maintenance and growth of microorganisms. 4.3 General Microbiological Methods. 4.4 Examples of Whole-cell Biotransformations using Bacteria. 4.5 Biotransformation by filamentous fungi and yeasts. 4.6 Whole-cell Biotransformations by recombinant strains of E. coli. 4.7 Conclusion. Chapter 5: A beginner’s guide to biotransformations by commercially available isolated enzymes. 5.1 Introduction. 5.2 Lipases. 5.3 Hydrolytic Reactions using lipases. 5.4 Using lipases for acylation reactions. 5.5 Other hydrolases. 5.6 Commercially available Coenzyme-dependent Enzymes. 5.7 Carbon-carbon bond forming reactions. 5.8 Conclusion. Chapter 6: A beginner’s guide to the isolation and analysis and use of home-grown enzyme biocatalysts. 6.1 Introduction. 6.2 Cell growth and harvesting. 6.3 Cell disruption. 6.4 A typical procedure for making a cell extract from a recombinant strain of E. coli. 6.5 Purification of enzymes - a brief guide. 6.6 Techniques for Protein Purification. 6.7 Isolation of recombinant enzymes using histidine tags. 6.8 Estimation of protein concentration. 6.9 Concentrating protein samples by centrifugation. 6.10 Analysis of protein samples by sodium dodecylsulfate polyacrylamide gel electrophoresis (SDS-PAGE). 6.11 Examples of enzyme assays. 6.12 Using home-grown enzymes for biotransformations ? Some recent examples. 6.13 Conclusion. Chapter 7: An introduction to basic gene cloning for the production of designer biocatalysts. 7.1 Introduction. 7.2 Background to gene cloning. 7.3 Gene amplification by polymerase chain reaction (PCR). 7.4 DNA fragment analysis by agarose electrophoresis. 7.5 Gene cloning. 7.6 Analysis by DNA sequencing. 7.7 Troubleshooting the gene amplification and cloning process. 7.8 Ligation-Independent Cloning. 7.9 Gene Expression in E. coli. 7.10 Conclusion. Chapter 8: Engineering Enzymes. 8.1 Introduction. 8.2 Site-directed or targted mutagenesis as a tool for investigating enzyme mechanism or altering catalytic attributes. 8.3 A site-directed mutagenesis experiment. Considerations and practise. 8.4 Engineering using random mutagenesis. Directed Evolution of Enzymes. 8.5 Combining rational and random mutagenesis for biocatalyst improvement. 8.6 Exploiting catalytic promiscuity for creating new enzyme activities. 8.7 Designing enzymes in silico. 8.8 Conclusion. Appendices. 1. Structures of the proteinogenic amino acids. 2. Structures of bases found in nucleic acids. 3. The Genetic Code. 4. Recipes for Microbiological Growth Media. 5. Biological buffers. 6. Ammonium sulphate fractionation table. 7. Restriction enzymes and restriction sites.

Read more less

Book SynopsisFor more than a century, bioactive heterocycles have formed one of the largest areas of research in organic chemistry. They are important from a biological and industrial point of view as well as to the understanding of life processes and efforts to improve the quality of life. Heterogeneous Catalysis: A Versatile Tool for the Synthesis of Bioactive Heterocycles highlights the recent methodologies used in the synthesis of such bioactive systems and focuses on the role of heterogeneous catalysis in the design and synthesis of various biologically active heterocyclic compounds of pharmacological interest. Topics include: Synthetic protocols for the construction of heterocyclic systems employing silica-bound catalysts Recent advances in heterogeneous copper-catalyzed reactions for the synthesis of bioactive heterocycles Features of silica-based heterogeneous catalysts, such as abundance, ease of use, and stabilityTable of ContentsSynthesis of Bioactive Heterocyclic Systems Promoted by Silica-Supported Catalysts. Eco-Benign Synthesis of Indole Derivatives Employing Diverse Heterogeneous Catalysts. Solid Heterogeneous Catalysts Based on Sulfuric Acid and Transition-Metal Salts: Synthesis of Bioactive Heterocycles. Heterogeneous Copper-Catalyzed Synthesis of Bioactive Heterocycles. Silica Sulfuric Acid: A Simple and Powerful Heterogeneous Catalyst in Organic Synthesis. Application of Silica-Based Heterogeneous Catalysis for the Synthesis of Bioactive Heterocycles. Application of Organometallic Compounds as Heterogeneous Catalysts in Organic Synthesis. Ultrasound: An Efficient Tool for the Synthesis of Bioactive Heterocycles. Nano–Zinc Oxide: An Efficient Heterogeneous Catalyst for the Synthesis of Heterocyclic Compounds. Application of Heterogeneous Catalysts for the Synthesis of Bioactive Coumarins. Silver: A Versatile Heterogeneous Catalyst for Heterocyclic Synthesis. Mesoporous Materials from Novel Silica Source as Heterogeneous Catalyst.

Read more less

Book Synopsis

Read more less

Book SynopsisThe chemical or biological process whereby the presence of an external compound, a catalyst, serves as an agent to cause a chemical reaction to occur or to improve reaction performance without altering the external compound. Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involve catalysis. Catalysis research is a major field in applied science, and involves many fields of chemistry and physics. The new book brings together leading research in this vibrant field.

Read more less

Book SynopsisThe chemical or biological process whereby the presence of an external compound, a catalyst, serves as an agent to cause a chemical reaction to occur or to improve reaction performance without altering the external compound. Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involve catalysis. Research into catalysis is a major field in applied science, and involves many fields of chemistry and physics. The book brings together leading research in this vibrant field.

Read more less

Book SynopsisThe chemical or biological process whereby the presence of an external compound, a catalyst, serves as an agent to cause a chemical reaction to occur or to improve reaction performance without altering the external compound. Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involve catalysis. Research into catalysis is a major field in applied science, and involves many fields of chemistry and physics. The new book brings together leading research in this vibrant field.

Read more less