Department of Chemistry, University of Science and Technology of China, Hefei 230026, People's Republic of China.
J Am Chem Soc. 2021 Aug 4;143(30):11309-11316. doi: 10.1021/jacs.1c05649. Epub 2021 Jul 20.
The practical synthesis of -stereogenic tertiary phosphines, which have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, represents a significant challenge. A regio- and enantioselective hydrophosphination using cheap and ubiquitous alkynes catalyzed by a nickel complex was designed, in which the toxic and air-sensitive secondary phosphines were prepared from bench-stable secondary phosphine oxides. This methodology has been demonstrated with unprecedented substrate scope and functional group compatibility to afford electronically and structurally diversified P(III) compounds. The products could be easily converted into various precursors of bidentate ligands and organocatalysts, as well as a variety of transition-metal complexes containing both and metal-stereogenic centers.
手性三级膦的实际合成在不对称催化、材料和药物化学等领域有广泛的应用，但这是一个重大的挑战。我们设计了一种使用镍配合物催化的区域和对映选择性氢膦化反应，其中有毒且对空气敏感的二级膦是由稳定的二级氧化膦制备得到的。该方法具有前所未有的底物范围和官能团兼容性，可以得到电子和结构多样化的 P(III)化合物。这些产物可以很容易地转化为各种双齿配体和有机催化剂的前体，以及含有 和金属手性中心的各种过渡金属配合物。
