NNN Pincer Ru(II)-Complex-Catalyzed alpha-Alkylation of Ketones with Alcohols

[Graphics] A series of novel ruthenium(II) complexes supported by a symmetrical NNN ligand were prepared and fully characterized. These complexes exhibited good performance in transfer hydrogenation to form new CC bonds using alcohols as the alkylating agents, generating water as the only byproduct. A broad range of substrates, induding (hetero)aryl- or alkyl-ketones and alcohols, were well tolerated under the optimized conditions. Notably, alpha-substituted methylene ketones were also investigated, which afforded alpha-branched steric hindrance products. A potential application of alpha-alkylation of methylene acetone to synthesize donepezil was demonstrated, which provided the desired product in 83% yield. Finally, this catalytic system could be applied to a one-pot double alkylation procedure with sequential addition of two different alcohols. The current protocol is featured with several characteristics, including a broad substrate scope, low catalyst (0.50 mol %) loadings, and environmental benignity.