Rh(III)-Catalyzed Divergent Synthesis of Alkynylated Imidazo[1,5-a]indoles and Α,α-Difluoromethylene Tetrasubstituted Alkenes.

Herein, we report the divergent synthesis of alkynylated imidazo[1,5-a]indoles and alpha,alpha-difluoromethylene tetrasubstituted alkenes through Rh(III)-catalyzed [4 + 1] annulation/alkyne moiety migration and C-H alkenylation/DG migration, respectively. This protocol features tunable product selectivity, excellent chemo-, regio-, and stereoselectivity, broad substrate scope, moderate to high yields, good tolerance of functional groups, and mild redox-neutral conditions.