Department of Chemistry, Texas Christian University, PO Box 298860, Fort Worth, Texas 76129, United States.
J Org Chem. 2020 Nov 20;85(22):14545-14558. doi: 10.1021/acs.joc.0c01151. Epub 2020 Aug 11.
Thiophosphorus acids RRP(S)OH constitute an important class of organophosphorus compounds, in which the phosphorus atom is intrinsically chiral if R ≠ R. In connection with a project aimed at the preparation of chiral thiophosphorus acids, various available literature methods were considered, but few fit the requirement of odorless reagents. Herein, the results of our studies on the synthesis of thiophosphinic acids are reported. Ultimately, two major approaches were selected: (1) the Stec reaction of phosphorus amides with carbon disulfide; and (2) the one-pot synthesis of thiophosphorus acids from -phosphinates, an organometallic nucleophile, and quenching with elemental sulfur. An application to the preparation of a potential chiral phosphorus organocatalyst is also reported.
硫代膦酸 RRP(S)OH 构成了一类重要的有机磷化合物，如果 R ≠ R，则磷原子本身就是手性的。在一个旨在制备手性硫代膦酸的项目中，我们考虑了各种现有的文献方法，但很少有方法符合无臭试剂的要求。在此，我们报告了关于硫代膦酸合成的研究结果。最终，选择了两种主要方法：（1）磷酰胺与二硫化碳的 Stec 反应；（2）-膦酸盐、有机金属亲核试剂和元素硫猝灭的一锅法合成硫代膦酸。还报告了在手性磷有机催化剂制备中的应用。
