Li Junchen, Gao Zhenhua, Guo Yongbiao, Liu Haibo, Zhao Peichao, Bi Xiaojing, Shi Enxue, Xiao Junhua
State Key Laboratory of NBC Protection for Civilian Beijing P. R. China
RSC Adv. 2022 Jun 29;12(29):18889-18896. doi: 10.1039/d2ra02908a. eCollection 2022 Jun 22.
Herein, a protocol for copper-catalyzed highly stereo- and regioselective hydrophosphorylation of terminal alkynes to -alkenylphosphorus compounds was well developed. It represents a general and practical hydrophosphorylation method, of which diarylphosphine oxide, dialkylphosphine oxide and dialkyl phosphite all had effective P(O)H parts to react with different types of terminal alkynes. Contrary to previous air-sensitive reports, all the reactions proceeded well under air. This methodology is quite attractive owing to the high stereo- and regioselectivity, good functional group tolerance, scalability and facile late-stage derivatization of some natural product derivatives and commercially available herbicides. What's more, investigations on the reaction mechanism with deuterium-labeling experiments and DFT studies firstly disclosed the deprotonation-protonation equilibrium of terminal alkynes and P(O)H part during the catalytic hydrophosphorylation process.
在此，一种用于铜催化末端炔烃高立体和区域选择性氢膦酰化反应生成α-烯基磷化合物的方法得到了很好的发展。它代表了一种通用且实用的氢膦酰化方法，其中二芳基氧化膦、二烷基氧化膦和亚磷酸二烷基酯都具有有效的P（O）H部分，可与不同类型的末端炔烃反应。与之前对空气敏感的报道相反，所有反应在空气中都能顺利进行。由于其高立体和区域选择性、良好的官能团耐受性、可扩展性以及对一些天然产物衍生物和市售除草剂的后期衍生化操作简便，该方法极具吸引力。此外，通过氘标记实验和密度泛函理论（DFT）研究对反应机理的研究首次揭示了催化氢膦酰化过程中末端炔烃和P（O）H部分的去质子化-质子化平衡。
