Chiral Amine Synthesis (2010)

Preface STEREOSELECTIVE SYNTHESIS OF ALPHA-BRANCHED AMINES BY NUCLEOPHILIC ADDITION OF UNSTABILIZED CARBANIONS TO IMINES Introduction Overview of the Methods for the Preparation of Imines Chiral Auxiliary-Based Approaches Catalytic Asymmetric Nucleophilic Addition to Achiral Imines Conclusion ASYMMETRIC METHODS FOR RADICAL ADDITION TO IMINO COMPOUNDS Background and Introduction Intermolecular Radical Addition Chiral N-Acylhydrazones Asymmetric Catalysis of Radical Addition Closing Remarks ENANTIOSELECTIVE SYNTHESIS OF AMINES BY CHIRAL BRONSTED ACID CATALYSTS Introduction Carbon-Carbon Bond Forming Reactions Carbon-Hydrogen Bond Forming Reactions Carbon-Heteroatom Bond Forming Reactions Conclusion REDUCTION OF IMINES WITH TRICHLOROSILANE CATALYZED BY CHIRAL LEWIS BASES Introduction Formamides as Lewis-Basic Organocatalysts in Hydrosilylation of Imines Other Amides as Organocatalysts in Hydrosilylation of Imines Sulfinamides as Organocatalysts in Hydrosilylation of Imines Supported Organocatalysts in Hydrosilylation of Imines Mechanistic Considerations Synthetic Applications Conclusions Typical Procedures for the Catalytic Hydrosilylation of Imines CATALYTIC, ENANTIOSELECTIVE VINYLOGOUS MANNICH REACTIONS Introduction Vinylogous Mukaiyama-Mannich Reactions of Silyl Dienolates Direct Vinylogous Mannich Reactions of Unmodified Substrates Miscellaneous Conclusion CHIRAL AMINES FROM TRANSITION-METAL-MEDIATED HYDROGENATION AND TRANSFER HYDROGENATION Scope and Related Publications Chiral Amines with a Disubstituted Nitrogen Atom, HNRR1 Chiral Amines with Trisubstituted Nitrogen, NRR1R2 Conclusion ASYMMETRIC REDUCTIVE AMINATION Introduction Transition Metal-Mediated Homogenous Reductive Amination Enantioselective Organocatalytic Reductive Amination Diastereoselective Reductive Amination Conclusions ENANTIOSELECTIVE HYDROGENATION OF ENAMINES WITH MONODENTATE PHOSPHORUS LIGANDS Introduction Asymmetric Hydrogenation of Enamides Asymmetric Hydrogenation of N,N-Dialkyl Enamines Conclusion and Outlook BIDENTATE LIGANDS FOR ENANTIOSELECTIVE ENAMIDE REDUCTION Introduction Catalytic Enantioselective Hydrogenation of Enamides Conclusions ENANTIOSELECTIVE REDUCTION OF NITROGEN-BASED HETEROAROMATIC COMPOUNDS Asymmetric Hydrogenation of Quinolines Asymmetric Hydrogenation of Isoquinolines Asymmetric Hydrogenation of Pyrroles Asymmetric Hydrogenation of Quinoxalines Asymmetric Hydrogenation of Pyridine Derivatives Summary and Outlook ASYMMETRIC HYDROAMINATION Introduction: Synthesis of Amines via Hydroamination Hydroamination of Simple, Nonactivated Alkenes Hydroamination of Dienes, Allenes, and Alkynes Hydroamination with Enantiomerical Pure Amines Synthesis of Chiral Amines via Tandem Hydroamination/Hydrosilylation Conclusions Experimental Section ENANTIOSELECTIVE C-H AMINATION Introduction Background Racemic C-H Amination Substrate-Controlled Chiral Amine Synthesis via C-H Amination Enantioselective C-H Amination of Achiral Substrates Conclusion CHIRAL AMINES DERIVED FROM ASYMMETRIC AZA-MORITA-BAYLIS-HILLMAN REACTION Introduction Recent Mechanistic Insights Asymmetric Aza-MBH Reaction Chiral Auxiliary-Induced Diastereoselective Aza-MBH Reaction Chiral Teriary Amine Catalysts Chiral Phosphine Catalysts Chiral Bifunctional N-Heterocyclic Carbenes Chiral Ionic Liquids as Reaction Medium Aza-MBH-Type Reaction to Obtain Chiral Amines Strategies for the Removal of Protecting Groups Selected Typical Experimental Procedures Summary and Outlook BIOCATALYTIC ROUTES TO NONRACEMIC CHIRAL AMINES Introduction Kinetic Resolution of Racemic Amines DKR and Deracemization of Amines Asymmetric Synthesis of Amines Using Transaminases Conclusions and Future Perspectives