Transition-Metal-Catalyzed Enantioselective Propargylic Substitution Reactions of Propargylic Alcohol Derivatives with Nucleophiles

Abstract

Recent advances in the transition-metal-catalyzed enantioselectivepropargylic substitution reactions of propargylic alcohol derivativeswith nucleophiles are reviewed in this article. After the disclosureof the first example of a ruthenium-catalyzed propargylic alkylation,various types of enantioselective propargylic substitution reactions,including enantioselective propargylation of aromatic compounds,have been reported in the last eight years. In addition, a varietyof enantioselective propargylic alkylations use two distinct catalysts,where the two catalysts work cooperatively to promote the asymmetricreactions. 1 Introduction 2 Ruthenium-Catalyzed Enantioselective Propargylic SubstitutionReactions 2.1 Propargylic Alkylation 2.2 Propargylation of Aromatic Compounds with Propargylic Alcohols 2.3 Propargylic Substitution Reactions of Propargylic Alcohols withAlkenes 2.4 Cycloadditions between Propargylic Alcohols and 2-Naphthols 3 Copper-Catalyzed Enantioselective Propargylic SubstitutionReactions 3.1 Propargylic Amination 3.2 Ring-Opening Reactions of Ethynyl Epoxides 3.3 Propargylic Alkylation 3.4 Propargylation of Indoles 4 Cooperative Enantioselective Propargylic Alkylations -UsingTransition-Metal Catalysts and Organocatalysts 4.1 With Ruthenium Catalysts 4.2 With Copper Catalysts 4.3 With Lewis Acid Catalysts 5 Cooperative Reactions Using Distinct Transition-Metal Catalysts 6 Miscellaneous Reactions 7 Conclusion