Transition‐Metal‐Free Carbonyl Reduction and Hydrodefluorination of β‐Trifluoromethyl Enones with Hydrosilanes: Synthesis of gem‐Difluorovinyl Alcohols

A transition‐metal‐free tandem carbonyl reduction and hydrodefluorination of b‐trifluoromethyl enones with hydrosilanes was developed for the synthesis of a variety of valuable gem‐difluorovinyl alcohols. The hydrosilane could act as both a reductive agent and a C(sp3)‐F bond‐breaking promotor under mild reaction conditions. Synthetically useful organofluorides, such as gem‐fluorophosphine alkene, gem‐difluorovinyl ketone, and fluorinated dihydrofuran derivatives could be constructed by the further transformations of the obtained gem‐difluorovinyl alcohols. Moreover, the method features operationally simple, excellent functional group tolerance, mild reaction conditions, and scalability.