Classics in Stereoselective Synthesis

This book provides a noteworthy compilation of the groundbreaking methods of stereoselective synthesis, belonging to the repertoire of every modern practitioner of synthetic organic chemistry. The general principles underlying these processes are highlighted as they form the basis for the rapid and continuing developments in the field. The work also features illustrative examples of drug and natural product syntheses, resulting in a rich source of stimulating ideas for the efficient use of asymmetric reactions in the construction of stereochemically complex structures. From the contents: "Macrocyclic stereocontrol "Carbonyl addition reactions "alpha-Functionalization of enolates "Aldol and allylation reactions "Chiral acetals "Alkene hydroboration, reduction, and oxidation "Additions to C=N bonds and synthesis of amino acids "Conjugate additions "Chiral carbanions "Metal-catalyzed allylations "Cyclopropanations and CH-insertion reactions "Sigmatropic rearrangements "Diels-Alder and hetero-Diels-Alder reactions "[3+2]- and [2+2]-cycloaddition reactions

Table of Contents:
MACROCYCLIC STEREOCONTROL Introduction Background Conformational Control in Medium-Sized Rings Asymmetric Synthesis with Medium-Sized Rings Case Studies in Natural Products Total Synthesis Macrocyclic Stereocontrol in Cyclic Peptides Appendix: Macrocycle Formation CARBONYL ADITION REACTIONS Introduction Non-Chelated 1,2-Asymmetric Induction and the Operation of Steric and Electronic Effects 1,2-Asymmetric Induction Predicated on Chelation Control 1,3-Asymmetric Induction from CBeta Stereogenic Centers Asymmetric Induction by Remote Stereocenters (Beyond 1,3-Induction) Catalytic Enantioselective Carbonyl Additions of Arganozinc Species Enantioselective Ketone Reduction Enzymatic Reduction of Ketones Enantioselective Formation of Cyanohydrins Enantioselective Alkyne Additions Asymmetric Carbonyl-Ene Reactions ALPHA-FUNCTIONALIZATIONS OF ENOLATES Introduction Diastereoselective Alpha-Alkylations of Chiral Enolates Heteroatom-Substituted Enolates Asymmetric Enolate Alkylations Using Chiral Auxiliaries Enantioselective Enolate Alkylations Alpha-Hydroxylations of Enolates Alpha-Halogenations of Enolates ALDOL REACTIONS Introduction Chiral Enolates Through the Use of Chiral Auxiliaries or Chiral Controller Groups Substrate Control with Chiral Carbonyl Compounds Catalytic Enantioselective Aldol Reactions ALLYLATIONS OF C=O BONDS Introduction Reactivity of Allylmetal Reagents Boronate Additions Enantioselective Additions of Optically Active Allylic Boron Reagents Diastereoselecive Allylations with Chiral Boron Reagents Mechanistic Aspects - Lewis Acid-Promoted Addition of Allylsilanes and Allylstannanes to Aldehydes Chelation Control in the Allylation of Alpha- and Beta-Alkoxy Aldehydes Allylchromium Reagents Diastereoselective Allylations with Chiral Silanes and Stannanes Catalytic Asymmetric Allylations CHIRAL ACETALS Introduction Diastereoselective Reactions of Chiral Acetals Glycosylations Spiroketals in Natural Product Synthesis ALKENE HYDROBORATION Introduction Hydroborations with Acyclic Stereocontrol Metal-Catalyzed Hydroborations Asymmetric Hydroborations with Chiral Boranes Catalytic Asymmetric Hydroboration, Hydrosilylation, and Hydroalumination REDUCTIONS OF OLEFINS Introduction Diastereoselective Olefin Reductions by Catalytic Hydrogenation Alternative Methods for Diastereoselective Olefin Reductions Catalytic Asymmetric Olefin Hydrogenations OXIDATIONS OF OLEFINS Introduction Diastereoselective Epoxidations Enantioselective Epoxidations Asymmetric Ring-Opening of Epoxides Synthesis of Aziridines Iodolactonizations and Other Olefin Cyclizations Induced by Electrophiles Diastereoselective Dihydroxylations of Olefins Enantioselective Dihydroxylations of Olefins Enantioselective Aminohydroxylation of Olefins AMINO ACIDS Introduction Enantioselective Hydrogenations of Alpha, Beta-Didehydroamino Acids Enolate Alkylations in the Presence of Chiral Auxiliaries Alkylation of Glycine Anion Equivalents in the Presence of Chiral Phase-Transfer Catalysts Enolate Aminations Enzymatic Syntheses of Alpha-Amino Acids Catalytic Asymmetric Strecker Reactions ADDITIONS TO C=N BONDS Introduction Substrate-Controlled Diastereoselective Additions to C=N Bonds Additions to Imine Derivatives Bearing N-Bound Auxiliaries Formation of Beta-Lactams Through Staudinger Reactions Intramolecular Diastereoselective Iminium Ion Cyclizations Pictet-Spengler Reactions Catalytic Asymmetric Reductions of Imines and Imine Derivatives Catalytic Enantioselective Mannich and Mannich-Type Reactions Enantioselective Additions of Carbon Nucleophiles to C=N Bonds CONJUGATE ADDITIONS Introduction Diastereoselective Conjugate Additions Diastereoselective Conjugate Additions with Use of Chiral Auxiliaries Enantioselective Conjugate Additions of Enolates and other Stabilized Carbon Nucleophiles Enantioselective Conjugate Additions of Organometallic Species Enantioselective Conjugate Additions of Radicals Enantioselective Conjugate Additions of Heteroatom Nucleophiles Conjugate Reductions Catalytic Enantioselective Stetter Reactions CHIRAL CARBONIONS Introduction Organolithium Reagents by Transmetalation of Organostannanes Carbanions by Reductive Methods Chiral Carbanions by Deprotonation Sulfoxide- and Phosphorus-Stabilized Carbanions Metal-Mediated Enantioselective Olefin Functionalizations METAL-CATALYZED ALLYLATIONS Introduction Diastereoselective Palladium-Catalyzed Allylation Reactions Enantioselective Palladium-Catalyzed Allylation Reactions Iridium-Catalyzed Enantioselective Allylation Reactions Copper-Catalyzed SN2' Allylation Reactions Enantioselective Allylation Reactions Catalyzed by Other Transition Metals Asymmetric Ring-Opening Reactions of Unsaturated Heterocycles CYCLOPROPANATIONS AND C-H INSERTION REACTIONS Introduction Diastereoselective Cyclopropanations with Carbenoids Generated from Diazoalkanes Enantioselective Dyclopropanations with Carbenoids Generated from Diazoalkanes Diastereoselective Simmons-Smith Cyclopropanations Enantioselective Simmons-Smith Cyclopropanations Alternative Classes Cyclopropanations Diastereoselective C-H Bonds SIGMATROPIC REARRANGEMENTS Introduction Claisen and Claisen-Type [3,3]-Sigmatropic Rearrangements Cope and Cope-Type [3,3]-Sigmatropic Rearrangements [2,3]-Sigmatropic Rearrangements Ene Reactions Nazarov Cyclizations DIELS-ALDER AND HETERO-DIELS-ALDER REACTIONS Introduction Diastereoselective Intermolecular Diels-Alder Reactions Diastereoselective Intramolecular Diels-Alder Reactions Diastereoselective Diels-Alder Reactions Using Chiral Auxiliaries Catalytic Enantioselective Diels-Alder Reactions Diastereoselective Hetero-Diels-Alder Reactions Enantioselective Hetero-Diels-Alder Reactions [3+2]- AND [2+2]-CYCLOADDITION REACTIONS Introduction Substrate-Controlled Diastereoselective [1,3]-Dipolar Cycloadditions Diastereoselective [1,3]-Dipolar Cycloadditions Using Chiral Auxiliaries Catalytic Enantioselective [1,3]-Dipolar Cycloadditions [3+2]-Cycloadditions with Trimethylenemethane Equivalents Ketene Cycloadditions Photochemical [2+2]-Cycloadditions