Catalytic Enantioselective Cyclopropenation of Internal Alkynes: Access to Difluoromethylated Three‐Membered Carbocycles

Herein we described an efficient Rh^II‐catalyzed enantioselective cyclopropenation reaction of internal alkynes with a masked difluorodiazoethane reagent (PhSO₂CF₂CHN₂, Ps‐DFA). This asymmetric transformation offers efficient access to a broad range of enantioenriched difluoromethylated cyclopropenes (40 examples, up to 99 % yield, 97 % ee). The synthetic utility of obtained strained carbocycles is demonstrated by subsequent stereodefined processes, including cross‐couplings, hydrogenation, Diels–Alder reaction, and Pauson–Khand reaction.