Silver-Catalyzed Asymmetric Desymmetrization of Cyclopentenediones via [3 + 2] Cycloaddition with α-Substituted Isocyanoacetates

Abstract

A highly selective and practical asymmetric Ag(I) catalyst system has been developed for the [3 + 2] cycloaddition reactions between isocyanoacetates and cyclopentenediones. The current Ag(I) catalyst system tolerates moisture and air and readily utilizes class III solvents such as EtOAc and acetone. The development of on demand generation of an active chiral catalyst in the presence of isocyanides paves a way to the efficient asymmetric preparation of bicyclic pyrrolidines with four stereogenic centers, including two quaternary centers in 80–97% ee.