Silver-Catalyzed Asymmetric Desymmetrization of Cyclohexadienones via Van Leusen Pyrrole Synthesis

Abstract

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 (<b>L</b>*), cyclohexadienone, and NasMIC.