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