Dynamic Stereochemistry of Chiral Compounds

"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) *

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. Knig. 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 SmithKline 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.

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. Cr