“On‐Water” Bisphosphorylation of β‐Trifluoromethyl Enones via Successive C(sp3)─F Bonds Functionalization: Synthesis of Multi‐Substituted Furans

Abstract The selective functionalization of C(sp 3 )─F bonds in accessible trifluoromethyl compounds is challenging but attractive. An “on‐water” defluorinative bisphosphorylation of β‐trifluoromethyl enones and phosphine oxides were developed for the modular synthesis of valuable multi‐substituted furans. This reaction proceeded through the successive functionalization of the trifluoromethyl group on enones, enabling the construction of one O ‐heterocycle, the formation of three C─P/C─O bonds, and the cleavage of three C(sp 3 )─F bonds under transition metal‐free reaction conditions. The aqueous solution also plays a unique role in determining the reaction reactivity and selectivity.