Selective Catalytic Synthesis of α-Alkylated Ketones and β-Disubstituted Ketones via Acceptorless Dehydrogenative CrossCoupling of Alcohols

Herein, a phosphine-free pincer ruthenium(III) catalyzed beta-alkylation of secondary alcohols with primary alcohols to alpha-alkylated ketones and two different secondary alcohols to beta-branched ketones are reported. Notably, this transformation is environmentally benign and atom efficient with H2O and H-2 gas as the only byproducts. The protocol is extended to gram-scale reaction and for functionalization of complex vitamin E and cholesterol derivatives.

Automated summary

A phosphine-free pincer ruthenium(III) catalyzed beta-alkylation of secondary alcohols with primary alcohols to alpha-alkylated ketones and beta-branched ketones from two different secondary alcohols is reported. This environmentally friendly and atom efficient transformation produces only H2O and H-2 gas as byproducts. The protocol has been successfully scaled up to gram-scale reactions and applied to the functionalization of complex vitamin E and cholesterol derivatives.