A catalytic
asymmetric desymmetrization of cyclohexadienones was
accomplished via Van Leusen pyrrole synthesis in the presence of a
chiral silver catalyst. The ready access to chiral-fused pyrrole derivatives
is attributed to the identification of a suitable isocyanomethyl sulfone
surrogate, NasMIC. The current Ag(I)–chiral phosphino-carboamide
ligand system can be extended to the kinetic resolution of racemic
cyclohexadienones, capitalizing on the differentiated reactivity of
chiral quaternary complexes from AgSbF6, chiral ligand
(L*), cyclohexadienone, and NasMIC.