Stereoselective Access to Trifunctionalized Z ‐Allylic Alcohols via Radical‐Mediated 1,4‐Aryl Migration

ABSTRACT Given the synthetic significance of allylic alcohols, developing efficient methods for their preparation remains a central pursuit in organic chemistry. Herein, we report a stereoselective approach to access trifunctionalized Z ‑allylic alcohols via a radical‑mediated 1,4‑aryl migration. By employing readily available benzyl propargyl ethers and Togni‐II reagent as the CF 3 source, this reaction proceeds through inert C(sp 2 )–C(sp 3 ) bond cleavage, enabling the modular assembly of valuable trifluoromethylated Z ‑allylic alcohols under mild, photoredox‑neutral conditions. The protocol exhibits a broad substrate scope, excellent functional‑group tolerance, and high regio‐ and stereo‐selectivity.