Allylation and Alkynylation of α‐Trifluoromethyl Alkyl Iodide Enabled by Photoredox Induced Halogen‐Atom‐Transfer

Abstract Herein, we report a visible‐light‐catalyzed protocol for the trifluoroalkylation of alkynyl sulfones/ allyl sulfones using readily available α‐trifluoromethyl haloalkanes. This reaction is driven by DIPEA as a halogen‐atom transfer (XAT) reagent, providing a new strategy to access valuable propargyl and homoallyl trifluoromethyl compounds via Csp─Csp 3 or Csp 3 ─Csp 3 bond formation. Notably, the methodology effectively suppresses the undesired β‐fluoride elimination of α‐trifluoromethyl radicals, thus avoiding the formation of gem‐difluoroalkenes. The transformation proceeds efficiently under mild conditions, affording the trifluoromethylated products in modest to excellent yields.