RuHCl(CO)(PPh₃)₃‑Catalyzed α‑Alkylation of Ketones with Primary Alcohols

The α-alkylation reaction of ketones with primary alcohols to give α-alkylated ketones was achieved using RuHCl(CO)(PPh₃)₃ as a catalyst in the presence of Cs₂CO₃ as a base. This reaction proceeds via an aldol condensation of ketones with aldehydes, formed via transfer dehydrogenation of alcohols, to give α,β-unsaturated ketones, which then undergo transfer hydrogenation with primary alcohols to give α-alkylated ketones and aldehydes, the latter of which participate in the next catalytic cycle. While the reaction of aliphatic primary alcohols was sluggish compared with that of benzylic alcohols, a catalytic amount of 1,10-phenanthroline was found to promote the alkylation dramatically