Kinetic Resolution of Spiroindolines through Ir-Catalyzed Asymmetric Allylative Ring-Opening Reaction.

Kinetic resolution of racemic spiroindolines with s factors of ≤15200 has been developed to access enantiomerically enriched indole-annulated medium-sized lactams and spiroindolines through Ir-catalyzed asymmetric allylative ring-opening reaction. Density functional theory calculations support the idea that the accurate discrimination of two spiroindoline enantiomers by (η3-allyl)-iridium(III) species and the perfect central-to-axial chirality conversion during C-C bond fragmentation ensure the stereoselective formation of two contiguous stereogenic centers and one axis in the medium-sized lactams.