Photoinduced <i>Gem</i>‐Difluoroallylic Ketones Formation via Selective Carbonyl – C(sp³) Bond Cleavage of <i>β</i>‐Ketone Alcohols

Abstract A photoinduced reaction for the formation of gem ‐difluoroallylic ketones via selective β ‐scission of β ‐ketone alcohols with α ‐trifluoromethyl alkenes is described. This process demonstrates a broad substrate scope for both β ‐ketone alcohols and α ‐trifluoromethyl alkenes. The reaction is proposed to proceed via an intramolecular PCET mechanism. The core of the strategy involves the oxidative cleavage of the carbonyl – C(sp 3 ) bond in β ‐ketone alcohols, facilitated by a base, to release acyl radicals, followed by the rapid addition of α ‐trifluoromethyl alkenes. Additionally, various downstream transformations were carried out with these compounds in a one‐step operation. This protocol is also applicable to corresponding alkynylation and Minisci reactions.