Selective Catalytic Synthesis of α‑Alkylated Ketones and β‑Disubstituted Ketones via Acceptorless Dehydrogenative Cross-Coupling of Alcohols

Herein, a phosphine-free pincer ruthenium­(III) catalyzed β-alkylation of secondary alcohols with primary alcohols to α-alkylated ketones and two different secondary alcohols to β-branched ketones are reported. Notably, this transformation is environmentally benign and atom efficient with H2O and H2 gas as the only byproducts. The protocol is extended to gram-scale reaction and for functionalization of complex vitamin E and cholesterol derivatives.