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

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 <i>on demand</i> 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