Rh(III)-Catalyzed Diastereodivergent Spiroannulation of Cyclic Imines with Activated Alkenes

Rh­(III)-catalyzed [3 + 2] annulation of cyclic N-sulfonyl or N-acyl ketimines with activated alkenes has been realized, leading to the synthesis of spirocycles with three continuous stereogenic centers. This atom-economic reaction proceeded efficiently under mild and redox-neutral conditions via a C–H activation pathway, and the coupling is diastereodivergent, with the diastereoselectivity being controlled by silver additives.