Faculty of Chemistry, Wrocław University of Science and Technology, ul. Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
Org Biomol Chem. 2021 Apr 7;19(13):2823-2846. doi: 10.1039/d1ob00124h. Epub 2021 Mar 12.
Chiral organophosphorus compounds, especially those containing C-stereogenic carbons in the proximity of the phosphorus atom, are known for their unique properties and have found wide applications that span from medicinal chemistry to enantioselective catalysis. However, the synthesis of such chiral molecules, especially with the precise control of stereochemistry at chiral carbon atoms, still remains a very challenging task. This review summarizes recent advances in the highly stereoselective formation of C- and, in some cases, also P-stereogenic organophosphorus compounds. The presented synthesis strategy is based on the use of H-P reagents bearing TADDOL, BINOL or a menthol moiety attached to the phosphorus atom and serving as a chiral auxiliary. Reactions of such chiral H-P species with different partners, e.g., alkenes, alkynes, imines, and carbonyl compounds, leading to structurally diverse chiral organophosphorus compounds with up to five chiral centers are comprehensively discussed. In each case, the stereochemical outcome of the reaction is influenced by the presence of the chiral alcohol used; therefore, the content of this review is compiled into sections with respect to the type of chiral alcohol attached to the phosphorus atom in the H-P species applied.
手性有机磷化合物，特别是那些在磷原子附近含有 C 手性碳原子的化合物，以其独特的性质而闻名，它们的应用范围广泛，从药物化学到对映选择性催化。然而，此类手性分子的合成，特别是对手性碳原子的立体化学的精确控制，仍然是一项极具挑战性的任务。这篇综述总结了近年来在 C 手性和某些情况下 P 手性有机磷化合物的高对映选择性形成方面的进展。所提出的合成策略基于使用带有 TADDOL、BINOL 或薄荷醇部分的 H-P 试剂，这些部分连接在磷原子上并作为手性助剂。这些手性 H-P 物种与不同的反应物（例如烯烃、炔烃、亚胺和羰基化合物）的反应，导致具有多达五个手性中心的结构多样的手性有机磷化合物的形成，对此进行了全面讨论。在每种情况下，反应的立体化学结果都受到所用手性醇的存在的影响；因此，这篇综述的内容是根据应用的 H-P 物种中连接在磷原子上的手性醇的类型来进行分类的。
