This 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, bevel gears, switches and motors, and topologically chiral assemblies such as catenanes and rotaxanes. Racemization and diastereomerization reactions of numerous chiral compounds are discussed as well as the principles, scope and compatibility of commonly used analytical techniques. Details of analytical methods are provided and discussed as well as topics relating to the design of fascinating topologically chiral assemblies and molecular technomimetic devices in the context of dynamic stereochemistry. Strategies and recent developments that address important synthetic challenges are presented and highlighted with hundreds of examples, applications and detailed mechanisms. This exceptional book includes: – More than 550 figures, schemes and tables illustrating mechanisms of numerous asymmetric reactions and stereomutations of chiral compounds – Technical drawings illustrating the conceptual linkage between macroscopic devices such as turnstiles, ratchets, brakes, bevel gears or knots and molecular analogs – More than 3000 references to encourage further reading and facilitate additional literature research – A comprehensive glossary with stereochemical definitions and terms which facilitate understanding and reinforce learning This book will be of particular interest to undergraduates, graduates and professionals working and researching in the fields of organic synthetic chemistry and analytical chemistry.
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CHAPTER 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
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Professor Christian Wolf graduated from the University of Hamburg, Germany in 1993 where he received his Ph.D. in 1995 under the auspices of Professor Wilfried A. König. After working as a postdoctoral Feodor-Lynen Fellow with Professor William H. Pirkle at the University of Illinois in Urbana, Illinois he took an R&D position at Smith Kline Beecham Pharmaceuticals, King of Prussia, Pennsylvania in 1997. In 2000, he accepted a position as Assistant Professor in the Chemistry Department at Georgetown University in Washington, DC where he was promoted to Associate Professor with tenure in 2006. He has been a visiting scholar at the University of Reading, England in 1991 and at the University of Aix-Marseille, France in 1995. Professor Wolf’s research interests comprise stereodynamics of chiral compounds, asymmetric synthesis, stereoselective sensing, chiral recognition, transition metal-catalyzed cross-coupling reactions, development of antimalarial drugs, and chiral chromatography.
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