Desulfurative Functionalization of β-Acyl Allylic Sulfides with N–H Free Indoles Highly Regioselective at C3 and N1 Positions: Rapid Access to α-Branched Enones

A regiodivergent allylation of 1H-indoles highly selectively at the C3 and N1 positions with β-acyl allylic sulfides through desulfurative C–C/C–N bond-forming reactions has been developed under mild conditions. Notably, the remarkable site-selective switch can be achieved by a delicate choice of solvents and bases. This cost-efficient method displays a broad substrate scope, good functional compatibility, and excellent site-selectivity, thus offering a divergent synthesis of indole substituted α-branched enones, which possess diverse potential opportunities for further applications and derivatization.