Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Alkyl-β-Ketoaldehydes via Dynamic Kinetic Resolution

Abstract

The (R,R)-Teth-TsDPEN-Ru(II) complex promoted the one-pot double C=O reduction of α-alkyl-β-ketoaldehydes through asymmetric transfer hydrogenation/dynamic kinetic resolution (ATH-DKR) under mild conditions. In this process, ten anti-2-benzyl-1-phenylpropane-1,3-diols (85:15 to 92:8 dr) were obtained in good yields (41–87%) and excellent enantioselectivities (>99% ee for all compounds). Notably, the preferential reduction of the aldehyde moiety led to the in situ formation of 2-benzyl-3-hydroxy-1-phenylpropan-1-one intermediates. These intermediates played a crucial role in enhancing both reactivity and stereoselectivity through hydrogen bonding.

Keywords

• 2-alkyl-1-phenylpropane-1,3-diols
• ATH-DKR
• Noyori–Ikariya catalysts
• ruthenium
• reduction
• asymmetric catalysis