The mild and selective aliphatic C(CO)-C(α) bond activation (CCA) of ketones was successfully achieved at room temperature using rhodium(ii) porphyrins in the presence of H2O. Rh(II)(tmp) (tmp = tetrakismesitylporphyrinate dianion) disproportionates in H2O to generate the highly reactive intermediate Rh(III)(tmp)(OH) for cleaving the C-C bond of ketone, giving up to 90% of Rh(III)(tmp)(COR) and the corresponding oxidized carbonyl product in up to 76% yield within 10 min. Substrate scopes cover aliphatic as well as aromatic ketones. Both isopropyl and cyclic ketones worked well.
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