手性有机膦化合物在配体、催化剂以及生物活性分子等领域有着广泛的应用. 因此, 通过不对称合成高效构建含P-手性核心骨架化合物吸引了众多化学家的深入研究, 为丰富手性有机膦配体库以及潜在药用活性分子已起到了至关重要的促进作用. 由于五价膦氧化物相对于三价有机膦化合物更稳定且可通过一步还原即可得到三价有机膦化合物, 针对P-手性五价膦氧化合物的不对称合成也因此尤为受到关注, 并快速发展. 基于此, 并针对已报道的相关综述的具体情况, 总结了近三年来不对称合成P-手性膦氧化物的进展, 依据合成策略的不同, 分为手性助剂协助分离、催化去对称化、催化不对称合成、催化动力学拆分或动态动力学不对称转化以及酶催化五个方面进行阐释与讨论.

Enantioenriched organophosphates are ubiquitous in a large array of chiral ligands, chiral catalysts and bioactive molecules. Over the past few decades, synthetic chemists have contributed substantial efforts to develop the efficient methodologies for the construction of P-chiral phosphine derivatives, considerably enriching the arsenal of chiral organophosphine ligands and the promising pharmaceutical molecules. Among them, a number of works are focused on the synthesis of P-chiral phosphine oxides because it is more stability than trivalent phosphines and the convenient reduction. In view of the rapid progress in this area and the currently available reviews, the progress in the last three years is summarized and discussed, namely from 2020 to 2022. The description of the synthetic strategy is divided into five segments, involving asymmetric induction, catalytic desymmetrization, catalytic asymmetric synthesis, catalytic kinetic resolution or dynamic kinetic asymmetric transformation, and enzyme catalysis.