Catalyst electronic polarizability and enantiomeric excess in asymmetric hydrogenation

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• 作者：Santanab Giri ; David Zhigang Wang ; Pratim Kumar Chattaraj
• 关键词：Electronic polarizability ; Asymmetric hydrogenation ; Linear free energy relationship ; Enantiomeric excess ; Rhodium– ; phosphine complex
• 刊名：Tetrahedron
• 出版年：2010
• 出版时间：19 June 2010
• 年：2010
• 卷：66
• 期：25
• 页码：4560-4563
• 全文大小：805 K

文摘

In the classical rhodium–diphosphine complexes-catalyzed asymmetric hydrogenation of enamide substrates, examination on the role of catalyst electronic polarizability in the origin of enantioselectivity reveals its linear free energy relationship with the product enantiomeric ratio that is much more pronounced than analogous correlation with steric effect in the same systems. From a conceptually novel scenario, this work suggests that the often-overlooked chiral catalyst local polarizability property may function as a controlling force in enantioselection thus has important implication in rational catalyst design.