Efficient alkylation of ketones with primary alcohols catalyzed by ruthenium(II)/P,N ligand complexes

An efficient catalytic system containing [RuCl 2 (η 6 -p-cymene)] 2 and one P,N ligand, N-diphenylphosphino-2-aminopyridine ( L1 ) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by 1 H NMR and ESI-MS reveals a stable cationic L1 -coordinated ruthenium hydride intermediate, identified as [Ru(η 6 -p-cymene)(κ 2 - L1 )H] + . Organic intermediates consistent with a three-step dehydrogenation , alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.