Catalytic Propargylic Substitution Reactions

Abstract

Abstract In sharp contrast to the well‐established transition metal‐ catalyzed allylic substitution reactions, the study of the corresponding propargylic substitution reactions has been quite limited for constructing carbon–carbon and carbon–heteroatom bonds at the propargylic position. However, during the last decade, general and useful catalytic reactions have been developed extensively. In this Review, we summarize recent advances in catalytic propargylic substitution reactions of propargylic alcohols and their derivatives with heteroatom‐ and carbon‐centered nucleophiles. In addition to a variety of transition metals, such as Ru, Re, Rh, Ir, Ni, Pd, Pt, and Cu, which form organometallic species as intermediates, several Lewis acids and Brønsted acids are also applicable as catalysts in these reactions. The reaction mechanism and the scope of nucleophiles that can be used depend on the nature of the catalysts. Some examples of enantioselective substitution reactions at the propargylic position are also described.