中科院上海有机化学所殷亮团队报道了铜（I）催化不对称合成P-手性氨基膦。相关研究成果发表在2022年1月25日出版的《德国应用化学》。

该文中，研究人员研究了二芳基膦和邻苯甲酰羟胺在铜（I）催化下的反应。在对称二芳基膦的情况下，高收率地制备了一系列氨基膦。在不对称二芳基膦的情况下，以铜（I）-（R，RP）-Ph-FOXAP络合物为手性催化剂，以高产率和高对映选择性合成了一系列P-手性氨基膦。基于一些控制实验和³¹P NMR研究，提出了铜（I）催化的不对称反应的双电子氧化还原机制，包括不对称二芳基膦的动态动力学不对称转化。

最后，通过H₂O₂氧化生成的一个具有代表性的P-手性磷酸酰胺以高产率转化为手性二芳基膦酸盐，并保持对映选择性，其能够进一步转化为各种P-手性叔膦酸盐。

附：英文原文

Title: Copper(I)-Catalyzed Asymmetric Synthesis of P-Chiral Aminophosphinites

Author: Yan-Bo Li, Hu Tian, Shuai Zhang, Jun-Zhao Xiao, Liang Yin

Issue&Volume: 2022-01-25

Abstract: Herein, a copper(I)-catalyzed reaction of diarylphosphines and  O  -benzoyl hydroxylamines is developed. In the cases of symmetrical diarylphosphines, a series of aminophosphinites is prepared in high yields. In the cases of unsymmetrical diarylphosphines, an array of  P  -chiral aminophosphinites is synthesized by using copper(I)-(  R  ,  R  P  )-Ph-FOXAP complex as a chiral catalyst in high yields with high enantioselectivity. Based on several control experiments and  31  P NMR studies, a two-electron redox mechanism involving the dynamic kinetic asymmetric transformation of unsymmetrical diarylphosphines is proposed for the copper(I)-catalyzed asymmetric reaction. Finally, one representative  P  -chiral phosphoric amide generated through the oxidation with H  2  O  2  is transformed to chiral diarylphosphinate in high yields with maintained enantioselectivity, which allows further transformations towards various  P  -chiral tertiary phosphines.

DOI: 10.1002/anie.202117760

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202117760