“On-water” defluorophosphorylation oftrifluoromethylated enones with phosphineoxides

Xue-Qiang Chu,^*aLi-Wen Sun,^aCheng Ma,^dJia-Wei Chen,^aYu-Lan Chen,^aShao-Fei Ni,^*dMing-Quan Zhu,^aJie Zhou,^*bMengtao Ma^cand Zhi-Liang Shen^*a

^aTechnical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis, Schoolof Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816,China. E-mail: xueqiangchu@njtech.edu.cn;ias_zlshen@njtech.edu.cn.

^bState Key Laboratory of Materials-Oriented Chemical Engineering, College ofBiotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing211816, China. E-mail: jayzhou@njtech.edu.cn.

^cDepartment of Chemistry and Materials Science, College of Science, NanjingForestry University, Nanjing 210037, China.

^dDepartment of Chemistry, Key Laboratory for Preparation and Application ofOrdered Structural Materials of Guangdong Province, Shantou University, Shantou,515063, China. E-mail: sfni@stu.edu.cn.

Abstract:The distinctive fluorine effects on “on-water” chemistry have remained less explored. In this work, an “on water” reaction ofβ-trifluoromethylated enones with phosphine oxides was developed for the preparationof highly functionalizedgem-difluorodienes with excellentZ-selectivity. The reaction occurred through awell-designed tandem phospha-Brook rearrangement and defluorination sequence under transition-metal-free conditions in water solution, which efficiently overcame some competitive side reactions,such as hydrodefluorination, 1,4-nucleophilic addition, and phosphorylation. The success was attributedto favorable H-bonding interactions at the water–organic phase boundary which could activate the substrates and enhance the reaction selectivity.

GreenChemistry2023,25,6489-6497. (Impact factor: 9.8)

论文链接：https://pubs.rsc.org/en/content/articlelanding/2023/GC/D3GC01565C