Saito Yuki, Cho Soo Min, Danieli Luca Alessandro, Matsunaga Akira, Kobayashi Shū
Department of Chemistry, School of Science, The University of Tokyo 7-3-1, Hongo, Bunkyo-ku Tokyo Japan
Chem Sci. 2024 Apr 17;15(21):8190-8196. doi: 10.1039/d4sc01401d. eCollection 2024 May 29.
In contrast to conventional methods that rely on stoichiometric activation of phosphonylating reagents, we have developed a highly efficient catalytic method for the synthesis of phosphite diesters using a readily available phosphonylation reagent and alcohols with environmentally benign Zn(ii) catalysts. Two alcohols could be introduced consecutively on the P center with release of trifluoroethanol as the sole byproduct, without any additive, under mild conditions. The products could be oxidized smoothly to access phosphate triesters. A range of alcohols, including sterically demanding and highly functionalized alcohols such as carbohydrates and nucleosides, can be applied in this reaction.
与依赖磷酰化试剂化学计量活化的传统方法不同，我们开发了一种高效的催化方法，使用易于获得的磷酰化试剂和醇类，在环境友好的锌（II）催化剂作用下合成亚磷酸二酯。在温和条件下，无需任何添加剂，两种醇可以依次引入到磷中心，同时释放出三氟乙醇作为唯一的副产物。产物可以顺利氧化得到磷酸三酯。一系列醇类，包括空间位阻大且高度官能化的醇类，如碳水化合物和核苷，都可应用于该反应。
