Rh(III)-Catalyzed C–H Bond Addition/Amine-Mediated Cyclization of Bis-Michael Acceptors

A Rh­(III)-catalyzed C–H bond addition/primary amine-promoted cyclization of bis-Michael acceptors is reported. The C–H bond addition step occurs with high chemoselectivity, and the subsequent intramolecular Michael addition, mediated by a primary amine catalyst, sets three contiguous stereocenters with high diastereoselectivity. A broad range of directing groups and both aromatic and alkenyl C–H bonds were shown to be effective in this transformation, affording functionalized piperidines, tetrahydropyrans, and cyclohexanes.