Li Congyu, Yuan Jing-Mei, Chen Wenqiang, He Yimiao, Huang Jun, Huang Yanmin, Xiao Qi, Sheng Jiarong, Huang Chusheng
Guangxi Key Laboratory of Natural Polymer Chemistry and Physics, Nanning Normal University, No. 175 East Mingxiu Road, Nanning, Guangxi, 530001, China.
School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, No. 15 Yucai Road, Guilin, Guangxi, 541004, China.
Chem Asian J. 2019 Aug 1;14(15):2584-2587. doi: 10.1002/asia.201900533. Epub 2019 Jul 3.
Defluorinative C(sp )-P bond formation of α-trifluoromethyl alkenes with phosphine oxides or phosphonates have been achieved under catalyst- and oxidant-free conditions, giving phosphorylation gem-difluoroalkenes as products. α-Trifluoromethyl alkenes bearing various of aryl substituents such as halogen, cyano, ester and heterocyclic groups are available in this transformation. The results of control experiments demonstrated that the mechanism of dehydrogenative/defluorinative cross-coupling reactions was not a radical route, but might be an S 2' process involving phosphine oxide anion.
在无催化剂和无氧化剂的条件下，实现了α-三氟甲基烯烃与氧化膦或膦酸酯的脱氟C(sp³)-P键形成，得到磷酸化偕二氟烯烃产物。在该转化反应中，可以使用带有各种芳基取代基（如卤素、氰基、酯基和杂环基团）的α-三氟甲基烯烃。对照实验结果表明，脱氢/脱氟交叉偶联反应的机理不是自由基途径，而可能是涉及氧化膦阴离子的S2'过程。
