Rhodium-Catalyzed Hydrofunctionalization: Enantioselective Coupling of Indolines and 1,3-Dienes

We communicate a strategy for the hydrofunctionalization of 1,3-dienes via Rh-hydride catalysis. Conjugated dienes are coupled to nucleophiles to demonstrate the feasibility of novel C–C, C–O, C–S, and C–N bond forming processes. In the presence of a chiral JoSPOphos ligand, hydroamination generates chiral allylic amines with high regio- and enantioselectivity. Tuning both the pKa and steric properties of an acid-additive is critical for enantiocontrol.