Remote Radical Trifluoromethylation: A Unified Approach to the Selective Synthesis of γ-Trifluoromethyl α,β-Unsaturated Carbonyl Compounds
Marina Briand, Linh Duy Thai, Flavien Bourdreux, Nicolas Vanthuyne, Xavier Moreau, Emmanuel Magnier, Elsa Anselmi, Guillaume Dagousset
Abstract
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 ·RF radical sources enables the generalization of the reaction to other perfluoroalkyl groups (RF = CF2H, C4F9). Importantly, an unprecedented enantioselective C(sp3)–H perfluoroalkylation process is disclosed.
Topics & Concepts
TrifluoromethylationChemistryTrifluoromethylSilylationCombinatorial chemistryEnantioselective synthesisOrganic chemistrySurface modificationCatalysisAlkylPhysical chemistryFluorine in Organic ChemistryRadical Photochemical Reactions