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HFIP‐Assisted Single C−F Bond Activation of Trifluoromethyl Ketones using Visible‐Light Photoredox Catalysis

Soumen Ghosh, Zheng‐Wang Qu, Suman Pradhan, Avisek Ghosh, Stefan Grimme, Indranil Chatterjee

2021Angewandte Chemie International Edition92 citationsDOI

Abstract

A visible light photoredox catalytic method for the selective cleavage of single strong C-F bond in trifluoromethyl ketones is reported. Single electron reduction of trifluoromethyl ketones generates difluoromethyl radicals which can be engaged in intermolecular C-C bond formation with N-methyl-N-arylmethacrylamides to furnish fluorine-containing oxindole derivatives in good yields. The reaction shows excellent chemoselectivity with good functional group tolerance under mild conditions. 1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) as a solvent plays a critical role for the selective single C-F bond cleavage. High-level DFT calculations are depicted to shed light on the mechanism.

Topics & Concepts

TrifluoromethylChemistryPhotochemistryRadicalPhotoredox catalysisChemoselectivityIntermolecular forceCatalysisBond cleavageFluorineVisible spectrumSingle bondFunctional groupSolventMedicinal chemistryAlkylPhotocatalysisOrganic chemistryMoleculeMaterials scienceOptoelectronicsPolymerFluorine in Organic ChemistryRadical Photochemical ReactionsCatalytic C–H Functionalization Methods