Photoredox‐Catalyzed Deoxygenation of Hexafluoroacetone Hydrate Enables Hydroxypolyfluoroalkylation of Alkenes

Abstract An unprecedented photoredox‐catalyzed phosphine‐mediated deoxygenation of hexafluoroacetone hydrate was established to accomplish the hydroxylpolyfluoroalkylation of electron‐deficient alkenes. A range of bis(trifluoromethyl)carbinols were facilely accessed by using readily available hexafluoroacetone hydrate, instead of toxic gaseous hexafluoroacetone. A range of electron‐deficient alkenes are tolerated, giving the corresponding hydro‐hydroxylpolyfluoroalkylated products in moderate to high yields. Remarkable features of this synthetic strategy include operational simplicity, mild reaction conditions, excellent regioselectivity, and broad functional group tolerance. The success of this strategy relies on the delicate utilization of aldehyde/ketone‐ gem ‐diol intrinsic equilibrium, which offers an innovated open‐shell pathway for the assembly of synthetically challenging polyfluoroalkylated scaffolds.