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

A tandem carbonyl reduction and hydrodefluorination of β‐trifluoromethyl enones with hydrosilanes under transition‐metal‐free conditions 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(sp 3 )‐F bond‐breaking promoter under mild reaction conditions. Synthetically useful organofluorides, such as gem ‐fluorophosphine alkene, gem ‐difluorovinyl ketone, and fluorinated dihydrofuran derivatives could be readily constructed by further transformations of the obtained gem ‐difluorovinyl alcohols. Moreover, the method features mild reaction conditions, operational simplicity, excellent functional group tolerance, and scalability.