Combining Hydrodefluorination and Defluorophosphorylation for Chemo- and Stereoselective Synthesis of gem-Fluorophosphine Alkenes

Ya-Fei Hu,^a Man-Hang Feng,^a Peng-Yuan Zhang,^a Hao Xu,^a Mengtao Ma,^b Zhi-Liang Shen,*^a and Xue-Qiang Chu*^a

^a Technical Institute of Fluorochemistry, Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China. E-mails: ias_zlshen@njtech.edu.cn; xueqiangchu@njtech.edu.cn.

^b Department of Chemistry and Materials Science, College of Science, Nanjing Forestry University, Nanjing 210037, China.

Abstract: A chemo-, regio-, and stereoselective reaction of trifluoromethyl enones, phenylsilane, and phosphine oxides through a sequential hydrodefluorination and defluorophosphorylation relay is developed for the synthesis of distinctive gem-fluorophosphine alkenes. This multi-component reaction occurred under transition-metal-free conditions with good functional group tolerance. Moreover, the pre-installed carbonyl auxiliary is important for tuning the reactivity of β-trifluoromethyl enones, thereby enabling controllable and selective functionalization of two fluorine atoms in trifluoromethylated enones.

Organic Letters 2023, 25, 6368-6373. (Impact factor: 5.2)

论文链接：https://pubs.acs.org/doi/10.1021/acs.orglett.3c02357