Copper-Catalyzed Strain-Driven Enantiospecific C–C Oxidative Addition

Herein, we report a copper-catalyzed, enantiospecific cross-coupling of <i>gem</i>-difluorocyclopropanes with anilines that furnishes branched fluoroallylamines. Combined experimental and computational studies provide compelling evidence for the oxidative addition of a C–C bond to copper, thereby establishing a new elementary step in copper catalysis.

Moreover, our findings reveal an unusual concerted substitution type reductive elimination for C–N bond formation that involves simultaneous C–F and N–H bond cleavage, bypassing conventional allylic metal intermediates and establishing a new mechanistic framework for allylation chemistry. The mechanistic principles demonstrated herein, including the pivotal C–C oxidative addition to copper and the concerted reductive elimination, pave the way for new strategies in catalytic C–C bond functionalization.