Luo Shihui, Yuan Xinzhu, Cheng Jiangtao, Yang Zhiping, Huang Zhongxing, Wang Jun Joelle
Department of Chemistry, Hong Kong Baptist University Kowloon Hong Kong China
Department of Chemistry, The University of Hong Kong Hong Kong China.
Chem Sci. 2025 Mar 18;16(16):7051-7056. doi: 10.1039/d5sc01453k. eCollection 2025 Apr 16.
Although enantioselective hydrofunctionalizations of nitrones are established for the synthesis of various types of chiral hydroxylamines, the asymmetric catalytic hydrophosphinylation of nitrones remains highly challenging. Herein, an efficient asymmetric hydrophosphinylation of nitrones, catalyzed by the dinuclear zinc catalyst derived from ProPhenol, is presented, accommodating a variety of nitrones and phosphine oxides. This approach successfully addresses the long-standing challenge of catalytic hydrophosphinylation of the C[double bond, length as m-dash]N bond, and offers an efficient and rapid access towards chiral α-hydroxyamino-phosphine oxides. Control experiments suggest that the oxide anion in the nitrone motif is crucial for the enantio-control.
尽管已确立了通过硝酮的对映选择性氢官能化反应来合成各种类型的手性羟胺，但硝酮的不对称催化氢膦酰化反应仍然极具挑战性。在此，我们报道了一种由ProPhenol衍生的双核锌催化剂催化的高效硝酮不对称氢膦酰化反应，该反应适用于多种硝酮和氧化膦。这种方法成功解决了C=N键催化氢膦酰化反应长期存在的难题，并为合成手性α-羟基氨基膦氧化物提供了一种高效且快速的途径。对照实验表明，硝酮结构中的氧负离子对于对映体控制至关重要。
