Stereospecific Preparations of <i>P</i>‑Stereogenic Phosphonothioates and Phosphonoselenoates

P-Stereogenic phosphonothioates and phosphonoselenoates were readily prepared utilizing RP-menthyl phenylphosphite 1 by two methods. The first method used elemental sulfur or selenium to react with 1, followed by alkylation of the intermediates with alkyl halides. The second used 1 to react with disulfide or diselenide. Both methods stereospecifically produced the title compounds in nearly quantitative yields under mild conditions. Stereospecific chalcogenation of the phosphoryl was proposed as the key step in these reactions.本研究采用两种方法，以RP-薄荷基苯基亚磷酸酯1为原料，即可便捷合成P-手性硫代膦酸酯（P-stereogenic phosphonothioates）与硒代膦酸酯（phosphonoselenoates）。第一种方法：先使单质硫或硒与1反应，再利用卤代烷烃对所得中间体进行烷基化；第二种方法：使1与二硫化物或二硒化物直接反应。两种方法均可在温和条件下，以近乎定量的产率立体专一地得到目标化合物。研究提出，上述反应的关键步骤为磷酰基的立体专一性硫族化。