Remote Radical Trifluoromethylation: A Unified Approach to the Selective Synthesis of γ-Trifluoromethyl α,β-Unsaturated Carbonyl Compounds.

Site-selective trifluoromethylation of silyl dienol ethers derived from α,β-unsaturated aldehydes, ketones, and amides was achieved for the first time in the remote γ position. This photoredox catalyzed process is quite general to compounds bearing many functionalities and is applicable to the late-stage functionalization of biorelevant molecules. The use of S -perfluoroalkyl sulfoximines as ·R F radical sources enables the generalization of the reaction to other perfluoroalkyl groups (R F = CF 2 H, C 4 F 9 ). Importantly, an unprecedented enantioselective C(sp 3 )-H perfluoroalkylation process is disclosed.