Pd-Catalyzed Asymmetric Dearomatization of Indoles via Decarbonylative Heck-Type Reaction of Thioesters.

We report herein a palladium-catalyzed ligand-promoted asymmetric dearomatization of indoles via the decarbonylation of thioesters and the subsequent reductive Heck reaction. This protocol provides a facile and efficient way to construct an aza-quaternary stereocenter at the C2 position of indolines. A variety of functional groups and substitutions could be well tolerated, affording the substituted indolines with high enantioselectivities.