Copper Catalyzed C(sp 3 )–H Bond Alkylation via Photoinduced Ligand-to-Metal Charge Transfer
2021; American Chemical Society; Volume: 143; Issue: 7 Linguagem: Inglês
10.1021/jacs.1c00687
ISSN1943-2984
AutoresSean M. Treacy, Tomislav Rovis,
Tópico(s)Oxidative Organic Chemistry Reactions
ResumoUtilizing catalytic CuCl2 we report the functionalization of numerous feedstock chemicals via the coupling of unactivated C(sp3)-H bonds with electron-deficient olefins. The active cuprate catalyst undergoes Ligand-to-Metal Charge Transfer (LMCT) to enable the generation of a chlorine radical which acts as a powerful hydrogen atom transfer reagent capable of abstracting strong electron-rich C(sp3)-H bonds. Of note is that the chlorocuprate catalyst is an exceedingly mild oxidant (0.5 V vs SCE) and that a proposed protodemetalation mechanism offers a broad scope of electron-deficient olefins, offering high diastereoselectivity in the case of endocyclic alkenes. The coupling of chlorine radical generation with Cu reduction through LMCT enables the generation of a highly active HAT reagent in an operationally simple and atom economical protocol.
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