Stereoselective synthesis of 7-epi-incarvilline.

The enantioselective synthesis of 7-epi-incarvilline for formal syntheses of (-)-incarvilline, (+)-incarvine C, and (-)-incarvillateine is described. The key features of our synthesis involve (1) stereoselective construction of the optically active bicyclic lactone utilizing Pd(0)-catalyzed allylic alkylation, (2) efficient transformation of the bridged bicyclic lactone to the key bicyclic lactam skeleton, and (3) stereoselective elaborations of two stereocenters via a substrate-controlled catalytic hydrogenation and a 1,4-addition.