Utilizing catalytic CuCl we report the functionalization of numerous feedstock chemicals via the coupling of unactivated C(sp)-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)-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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| http://dx.doi.org/10.1021/jacs.1c00687 | DOI Listing |
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