Angewandte Chemie International Edition · 2019 · 200 citations · 53 references
Natural SciencesChemistryCatalysisGreen ChemistryOrganometallic ChemistryCoordination ChemistryCross-coupling ReactionsRadical ReactionsAtom Transfer CatalysisHydrogen Atom TransferMild Reaction ConditionsRadical MechanismsRadical Mediated C - H FunctionalizationTransition Metal-catalyzed SynthesisTransition-metal-catalyzed Functionalization
Abstract Reported herein is an unprecedented protocol for trifluoromethylation of unactivated aliphatic C(sp 3 )−H bonds. With Cu(OTf) 2 as the catalyst, the reaction of N‐fluoro‐substituted carboxamides (or sulfonamides) with Zn(CF 3 ) 2 complexes provides the corresponding δ‐trifluoromethylated carboxamides (or sulfonamides) in satisfactory yields under mild reaction conditions. A radical mechanism involving 1,5‐hydrogen atom transfer of N‐radicals followed by CF 3 ‐transfer from Cu II −CF 3 complexes to the thus formed alkyl radicals is proposed.
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Catalytic alkylation of remote C–H bonds enabled by proton-coupled electron transfer
Gilbert J. Choi, Qilei Zhu, David C. Miller et al. · Nature · 2016 · 770 citations · Full text