Defluorinative C(sp3)‒P Bond Construction for the Synthesis of Phosphorylation gem‐Difluoroalkenes under Catalyst‐ and Oxidant‐Free Conditions

: Defluorinative C(sp3 )-P bond formation of α-trifluoromethyl alkenes with phosphine oxides or phosphonates have been achieved under catalyst- and oxidant-free conditions, giving phosphorylation gem-difluoroalkenes as products. α-Trifluoromethyl alkenes bearing various of aryl substituents such as halogen, cyano, ester and heterocyclic groups are available in this transformation. The results of control experiments demonstrated that the mechanism of dehydrogenative/defluorinative cross-coupling reactions was not a radical route, but might be an SN 2' process involving phosphine oxide anion.