Open AccessCopper Catalyzed C(sp3)–H Bond Alkylation via Photoinduced Ligand-to-Metal Charge Transfer
Author(s) -
Sean M. Treacy,
Tomislav Rovis
Publication year - 2021
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c00687
Subject(s) - chemistry , reagent , catalysis , ligand (biochemistry) , alkylation , photochemistry , hydrogen atom , electron transfer , metal , combinatorial chemistry , organic chemistry , biochemistry , alkyl , receptor
Utilizing catalytic CuCl 2 we report the functionalization of numerous feedstock chemicals via the coupling of unactivated C(sp 3 )-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(sp 3 )-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.