The efficient construction of γ-chirogenic amines has been realized via asymmetric hydrogenation of γ-branched N-phthaloyl allylamines by using a bisphosphine-Rh catalyst bearing a large bite angle. The desired products possessing different γ-substituents were obtained in quantitative yields and with excellent enantioselectivities (up to >99% ee). This protocol provides a practical method for the preparation of γ-chirogenic amine derivatives such as the famous antidepressant drug Fluoxetine (up to 50000 S/C). The mechanistic calculations show an unusual P-Rh-P trans-chelating pattern and a weak interaction-promoted activation mode which are completely different from the traditional cis-chelating pattern and coordination-promoted activation mode in metal-catalyzed hydrogenations.

中文翻译：

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γ-支链烯丙胺的不对称氢化用于有效合成γ-手性胺

通过使用具有大咬合角的双膦-Rh催化剂，通过γ-支链N-邻苯二甲酰基烯丙胺的不对称氢化，实现了γ-手性胺的有效构建。以定量产率和优异的对映选择性（高达> 99％ee）获得了具有不同γ-取代基的所需产物。该协议为γ-手性胺衍生物的制备提供了一种实用的方法，例如著名的抗抑郁药氟西汀（高达 50000 S/C）。机理计算显示了与传统的完全不同的不寻常的 P-Rh-P反式螯合模式和弱相互作用促进的激活模式。金属催化氢化中的顺式螯合模式和配位促进的活化模式。