Key Laboratory of Preclinical Study for New Drugs of Gansu Province, School of Medicine, State Key Laboratory of Applied Organic Chemistry, and Institute of Biochemistry and Molecular Biology, Lanzhou University, Lanzhou 730000, PR China.
J Org Chem. 2010 Oct 15;75(20):6756-63. doi: 10.1021/jo1014917.
A catalyst was synthesized on the basis of Trost's dinuclear catalyst characterized by working well without pyridine in the present phospha-Michael reaction. Nevertheless, the presence of pyridine is still advantageous in the present system. The substrate scope was successfully extended to enones employing diallyl phosphine oxide as a nucleophile. Excellent yields and enantioselectivities (up to >99% ee) were achieved for a wide scope of enones employing the catalyst under mild conditions. The detailed reaction mechanism is also discussed herein. Finally, the unprecedented asymmetric additions of dialkylphosphine oxides to N-sulfinylimines were achieved by using Et(2)Zn as a base.
基于特罗斯特双核催化剂，我们合成了一种催化剂，其特点是在目前的膦迈克尔反应中无需吡啶即可很好地发挥作用。然而，吡啶的存在在目前的体系中仍然是有利的。该底物范围成功扩展到烯酮，采用二烯丙基氧化膦作为亲核试剂。在温和条件下，使用该催化剂可获得广泛范围的烯酮的优异产率和对映选择性（高达>99%ee）。本文还讨论了详细的反应机理。最后，通过使用 Et(2)Zn 作为碱，实现了二烷基氧化膦对 N-亚磺酰亚胺的空前不对称加成。
