Description
Book SynopsisThis book provides an overview of fundamental concepts of asymmetric synthesis highlighting the significance of stereochemical and stereodynamic reaction control. Topics include kinetic resolution (KR), dynamic kinetic resolution (DKR), dynamic kinetic asymmetric transformation (DYKAT), and dynamic thermodynamic resolution (DTR). In-depth discussions of asymmetric synthesis with chiral organolithium compounds, atropisomeric biaryl synthesis, self-regeneration of stereogenicity (SRS), chiral amplification with chiral relays and other commonly used strategies are also provided. Particular emphasis is given to selective introduction, interconversion and translocation of central, axial, planar, and helical chirality. A systematic coverage of stereochemical principles and stereodynamic properties of chiral compounds guides the reader through the book and establishes a conceptual linkage to asymmetric synthesis, molecular devices that resemble the structure and stereomutations of propellers,
Trade Review"This is a fresh approach which will be of some interest to process chemists and engineers who are not only interested in synthesis but also in kinetics and rates of processes." * Organic Process Research and Development, 2010, 14, 298 *
"This book provides a feast of fascinating chemistry involving wide-ranging stereochemical studies.""This is a book that people will love to read. The topics are well chosen and interesting and the writing is succinct and accurate. It could be used as a textbook for an advanced undergraduate or graduate special topics course and will serve as a valuable source of stimulating supplementary material for many courses." * Journal of the American Chemical Society *
It is presented in a way which gives a uniquely bright outlook and lays down a contemporary, concise, coherent and entertaining romp through dynamic stereochemistry.....is well produced, very clear and readable, with a particularly comfortable format.I would recommend the work for advanced students - masters and doctoral stage researchers - as well as the broad-minded professional. * Chemistry World, April 2008, 75-76 (David Amabilino) *
Table of ContentsCHAPTER 1: Introduction: CHAPTER 2: Principles of Chirality and Dynamic Stereochemistry; 2.1. Stereochemistry of chiral compounds; 2.2. Dynamic stereochemistry of cyclic and acyclic chiral compounds; CHAPTER 3: Racemization, Enantiomerization and Diastereomerization; 3.1. Classification of isomerization reactions of chiral compounds; 3.1.1. Racemization; 3.1.2. Enantiomerization; 3.1.3. Diastereomerization; 3.1.4. Epimerization and mutarotation; 3.2. Stereomutations of chiral compounds: Mechanisms and energy barriers; 3.2.1. Alkanes; 3.2.2. Alkenes and annulenes; 3.2.3. Allenes and cumulenes; 3.2.4. Helicenes and phenanthrenes; 3.2.5. Alkyl halides, nitriles and nitro compounds; 3.2.6. Amines; 3.2.7. Aldehydes, ketones and imines; 3.2.8. Alcohols, ethers, acetals, and ketals; 3.2.9. Carboxylic acids and derivatives; 3.2.10. Amino acids; 3.2.11. Silicon, phosphorus and sulfur compounds; 3.2.12. Organometallic compounds; 3.2.13. Supramolecular structures; 3.3. Atropisomerization; 3.3.1. Biaryls, triaryls and diarylacetylenes; 3.3.2. Nonbiaryl atropisomers; 3.3.3. Cyclophanes; 3.3.4. Atropisomeric xenobiotics; 3.4. Pharmacological and pharmacokinetic significance of racemization; CHAPTER 4: Analytical Methods; 4.1. Chiroptical methods; 4.2. Variable-temperature NMR spectroscopy and proton/deuterium exchange measurements; 4.3. Dynamic chromatography; 4.3.1. Dynamic high performance liquid chromatography; 4.3.2. Dynamic gas chromatography; 4.3.3. Dynamic supercritical fluid chromatography and electrokinetic chromatography; 4.4. Chromatographic and electrophoretic stopped-flow analysis; 4.5. Comparison of analytical methods; CHAPTER 5: Principles of Asymmetric Synthesis; 5.1. Classification of asymmetric reactions; 5.2. Kinetic and thermodynamic control; 5.3. Asymmetric induction; 5.3.1. Control of molecular orientation and conformation; 5.3.2. Single and double stereodifferentiation; CHAPTER 6: Asymmetric Synthesis with Stereodynamic Compounds: Introduction, Conversion and Transfer of Chirality; 6.1. Asymmetric synthesis with chiral organolithium reagents; 6.1.1. -Alkoxy- and -amino-substituted organolithium compounds; 6.1.2. Sulfur-, phosphorus- and halogen-stabilized organolithium compounds; 6.2. Atroposelective synthesis of axially chiral biaryls; 6.2.1. Intramolecular atroposelective biaryl synthesis; 6.2.2. Intermolecular atroposelective biaryl synthesis; 6.2.3. Atroposelective ring construction; 6.2.4. Desymmetrization of conformationally stable prochiral biaryls; 6.2.5. Asymmetric transformation of stereodynamic biaryls; 6.3. Nonbiaryl atropisomers; 6.4. Chirality transfer and interconversion of chiral elements; 6.4.1. Chirality transfer in SN2' and SE2' reactions; 6.4.2. Rearrangements; 6.4.2.1. 1,2-Chirality transfer; 6.4.2.2. 1,3-Chirality transfer; 6.4.2.3. 1,4-Chirality transfer; 6.4.2.4. 1,5-Chirality transfer; 6.4.3. Intermolecular chirality transfer; 6.4.4. Transfer of stereogenicity between carbon and heteroatoms; 6.4.5. Conversion of central chirality to other chiral elements; 6.4.6. Conversion of axial chirality to other chiral elements; 6.4.7. Conversion of planar chirality to other chiral elements; 6.5. Self-regeneration of stereogenicity and chiral relays; 6.5.1. Stereocontrolled substitution at a chiral center; 6.5.2. Self-regeneration of stereocenters; 6.5.3. Self-regeneration of chiral elements with stereolabile intermediates; 6.5.4. Chiral relays; 6.6. Asymmetric catalysis with stereolabile ligands; 6.6.1. Stereodynamic achiral ligands; 6.6.2. Stereolabile axially chiral ligands; 6.7. Stereoselective synthesis in the solid state; CHAPTER 7: Asymmetric Resolution and Transformation of Chiral Compounds under Thermodynamic and Kinetic Control; 7.1. Scope and principles of asymmetric resolution and transformation; 7.2. Asymmetric transformation of the first kind; 7.3. Asymmetric transformation of the second kind; 7.3.1. Crystallization-induced asymmetric transformation; 7.3.2. Asymmetric transformation based on chromatographic separation; 7.4. Kinetic resolution and dynamic kinetic resolution; 7.4.1. Kinetic resolution; 7.4.1.1. Enzyme-catalyzed kinetic resolution; 7.4.1.2. Nonenzymatic kinetic resolution; 7.4.1.3. Parallel kinetic resolution; 7.4.2. Dynamic kinetic resolution; 7.4.2.1. Enzyme-catalyzed dynamic kinetic resolution; 7.4.2.2. Nonenzymatic dynamic kinetic resolution; 7.5. Dynamic kinetic asymmetric transformation; 7.6. Dynamic thermodynamic resolution; CHAPTER 8: From Chiral Propellers to Unidirectional Motors; 8.1. Stability and reactivity of stereodynamic gears; 8.2. Structure and ring flipping of molecular propellers; 8.3. Dynamic gearing in biaryl-, triaryl- and tetraaryl propellers; 8.4. Molecular bevel gears; 8.5. Vinyl propellers; 8.6. Propeller-like coordination complexes with helicity control; 8.7. Static gearing and cyclostereoisomerism; 8.8. Molecular brakes, turnstiles and scissors; 8.9. Chiral molecular switches; 8.10. Stereodynamic sensors; 8.11. Chiral molecular motors; CHAPTER 9: Topological Isomerism and Chirality; 9.1. Synthesis of catenanes and rotaxanes; 9.1.1. Statistical methods; 9.1.2. Template-assisted assembly; 9.1.3. Topological isomerization; 9.2. Chiral catenanes; 9.3. Chiral rotaxanes; 9.4. Knots and Borromean rings; 9.5. Topological isomerism of shuttles, switches, sensors, and rotors; GLOSSARY: Stereochemical Definitions and Terms
