Room temperature carbon(CO)–carbon(α) bond activation of ketones by rhodium(ii) porphyrins with water

Abstract

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.