Asymmetric hydrogenation of N-alkyl and N-aryl ketimines using chiral cationic Ru(diamine) complexes as catalysts: the counteranion and solvent effects, and substrate scope

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• 作者：Fei Chen ; Ziyuan Ding ; Yanmei He ; Jie Qin ; Tianli Wang ; Qing-Hua Fan ; ^{fanqh@iccas.ac.cn}
• 关键词：Asymmetric catalysis ; Hydrogenation ; Ruthenium ; Ketimines ; Diamine ligand
• 刊名：Tetrahedron
• 出版年：2012
• 期刊代码：107_00404020
• 类别：ch
• 出版时间：1 July, 2012
• 卷：68
• 期：26
• 页码：5248-5257
• 文件大小：816 K

摘要

Asymmetric hydrogenation of N-alkyl and N-aryl ketimines catalyzed by chiral cationic η⁶-arene-(N-monosulfonylated diamine) Ru(II) complexes has been investigated. Strong counteranion and solvent effects on the enantioselectivity were observed. The ruthenium catalyst bearing non-coordinating BArF^? anion was found to be particularly effective for the hydrogenation of acyclic and exocyclic N-alkyl ketimines in the presence of (Boc)₂O in dichloromethane or even under solvent-free conditions, providing chiral amines with up to >99%ee and full conversions. Alternatively, the ruthenium catalyst bearing achiral phosphate anion together with corresponding phosphoric acid as the additive was also efficient for the hydrogenation of N-alkyl ketimines in the absence of (Boc)₂O with excellent enantioselectivities and full conversions. For N-aryl ketimines lower enantiomeric excesses were observed by using the ruthenium catalyst bearing BArF^? anion. This catalytic protocol thus provides a facile and practical access to optically active amines and has been successfully employed in the gram-scale synthesis of enantiomerically pure (+)-sertraline.