Cinchona Alkaloids in Synthesis and Catalysis

AN OVERVIEW OF CINCHONA ALKALOIDS IN CHEMISTRY
Brief History
Active Sites in Cinchona Alkaloids and Their Derivatives
Structural Information on Cinchona Alkaloids
How This Book is Organized

PART I: Cinchona Alkaloid Derivatives as Chirality Inducers in Metal-Catalyzed Reactions

CINCHONA ALKALOIDS AS CHIRALITY TRANSMITTERS IN METAL-CATALYZED ASYMMETRIC REDUCTIONS
Introduction
Homogeneous Systems for Ketone Reductions
Heterogeneous Pt and Pd Catalysts Modified with Cinchona Alkaloids
Industrial Applications
Conclusions
CINCHONA ALKALOIDS AS CHIRAL LIGANDS IN ASYMMETRIC OXIDATIONS
Introduction
Asymmetric Dihydroxylation of Alkenes
Aminohydroxylation
Sulfur Oxidations
Summary
CINCHONA ALKALOIDS AND THEIR DERIVATIVES AS CHIRALITY INDUCERS IN METAL-PROMOTED ENANTIOSELECTIVE CARBON-CARBON AND CARBON-HETEROATOM BOND FORMING REACTIONS
Introduction
Nucleophilic Addition to Carbonyl or Imine Compounds
Miscellaneous Reactions
Cinchona-Based Chiral Ligands in C-F Bond Forming Reactions
Conclusions

PART II: Cinchona Alkaloid Derivatives as Chiral Organocatalysts

CINCHONA-BASED ORGANOCATALYSTS FOR ASYMMETRIC OXIDATIONS AND REDUCTIONS
Introduction
Cinchona-Based Organocatalysts in Asymmetric Oxidations
Cinchona-Based Organocatalysts in Asymmetric Reductions
Conclusions
CINCHONA-CATALYZED NUCLEOPHILIC ALPHA-SUBSTITUTION OF CARBONYL DERIVATIVES
Introduction
Organocatalytic Nucleophilic Alpha-Substitution of Carbonyl Derivatives
Cinchona Alkaloids in Asymmetric Organocatalysis
The Pioneer Works for Phase-Transfer Catalytic Alpha-Substitution
Alpha-Substitution of Alpha-Amino Acid Derivatives via PTC
Alpha-Substitution of Other Carbonyl Derivatives via PTC
Alpha-Heteroatom Substitution via PTC
Nucleophilic Alpha-Substitution of Carbonyl Derivatives via Non-PTC
Conclusions
CINCHONA-MEDIATED ENANTIOSELECTIVE PROTONATIONS
Introduction
Preformed Enolates and Equivalents
Nucleophilic Addition on Ketenes
Michael Additions
Enantioselective Decarboxylative Protonation
Proton Migration
Summary of Cinchona-Mediated Enantioselective Protonations
CINCHONA-CATALYZED NUCLEOPHILIC 1,2-ADDITION TO C=O AND C=N BONDS
Introduction
Aldol and Nitroaldol (Henry) Reactions
Mannich and Nitro-Mannich Reactions
Aldol- and Mannich-Related Reactions
Cyanation Reactions
Trifluoromethylation
Friedel-Crafts Type Alkylation
Hydrophosphonylation
Conclusions
CINCHONA-CATALYZED NUCLEOPHILIC CONJUGATE ADDITION TO ELECTRON-DEFICIENT C=C DOUBLE BONDS
Introduction
Conjugate Reaction of Alpha,Beta-Unsaturated Ketones, Amides, and Nitriles
Conjugate Addition of Nitroalkenes
Conjugate Addition of Vinyl Sulfones and Vinyl Phosphates
Cyclopropanation and Other Related Reactions
Conclusions
CINCHONA-CATALYZED CYCLOADDITION REACTIONS
Introduction
Asymmetric Cycloadditions Catalyzed by Quinuclidine Tertiary Amine
Asymmetric Cycloadditions Catalyzed by Bifunctional Cinchona Alkaloids
Asymmetric Cycloaddition Reactions Catalyzed by Cinchona-Based Primary Amines
Asymmetric Cycloaddition Catalyzed by Cinchona-Based Phase-Transfer Catalysts
Conclusion
CINCHONA-BASED ORGANOCATALYSTS FOR DESYMMETRIZATION OF MESO-COMPOUNDS AND (DYNAMIC) KINETIC RESOLUTION OF RACEMIC COMPOUNDS
Introduction
Desymmetrization of meso-Compounds
(Dynamic) Kinetic Resolution of Racemic Compounds
Conclusions

PART III: Organic Chemistry of Cinchona Alkaloids

ORGANIC CHEMISTRY OF CINCHONA ALKALOIDS
Introduction
Preparation of Quincorine and Quincoridine: Discovery of a Novel Cleavage Reaction of Cinchona Alkaloids
Transformations of the Quinoline Moiety
Basic Transformations of the Vinyl Side Chain
Selected Novel Transformations of the Quinuclidine Moiety of Cinchona Alkaloids
Nucleophilic Substitution at Carbon C9
Novel Rearrangements of the Azabicyclic Moiety
General Experimental Hints and Obstacles
Conclusions

PART IV: Cinchona Alkaloid and Their Derivatives in Analytics

RESOLUTION OF RACEMATES AND ENANTIOSELECTIVE ANALYTICS BY CINCHONA ALKALOIDS AND THEIR DERIVATIVES
Introduction
Resolution of Racemates by Crystallization and Extraction of Diastereoisomers
Enantioselective Chromatography and Related Techniques
Cinchona Alkaloids as Chiral Solvating (Shift) Agents in NMR Spectroscopy
Cinchona-Based Sensors, Receptors, and Materials for Separation and Analytics