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

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(sp³) 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.