1,2-Dichloroethane-Assisted Defluorinative Ring-Opening Reaction of DABCO and Polyfluoroalkyl Peroxides:Synthesis of Fluorinated N-Ethyl Piperazines  

作　　者：Yuan-Yuan Ren Wen-Jun Ji Chi Zhang Danhua Ge Mengtao Ma Zhi-Liang Shen Xue-Qiang Chu 

机构地区：[1]Technical Institute of Fluorochemistry,Schoolof Chemistry and Molecular Engineering,Nanjing Tech University,Nanjing,Jiangsu 21186,China [2]Department of Chemistry and Materials Science,College of Science,Nanjing Forestry University,Nanjing,Jiangsu 210037,China

出　　处：《Chinese Journal of Chemistry》2025年第4期378-384,共7页中国化学(英文版)

基　　金：the financial support from the National Natural Science Foundation of China(22001121);Nanjing Tech University。

摘　　要：A catalyst-free and additive-free ring-opening reaction of polyfluoroalkyl peroxides,triethylenediamine(DABCO),and 1,2-dichloroethane(DCE)has been developed for the defluorinative synthesis of structurally diverse piperazines featuring a fluoroenone framework and a N-chloroethyl-substituent with high Z-stereoselectivity.The success of this three-component reaction is attributed to the in situ generation of an active 1-(2-chloroethyl)-1,4-diazabicyclo[2.2.2]octan-1-ium(DABCO·DCE)salt,which judiciously acts as a formal N-(2-chloroethyl)piperazine equivalent in the defluorinative coupling with less-studied aliphatic fluorinated substances.Impressively,this reaction accomplishes multi-activation of robust C(sp^(3))-F,C(sp^(3))-Cl,C(sp^(3))-O,and C(sp^(3))-N bonds in a one-pot process,offering a practical platform for the late-stage functionalization of complex molecules.Furthermore,the resulting products can not only serve as versatile building blocks for the synthesis of fluorinated heterocycles,but also undergo C—Cl bond displacement transformations with N-,O-,and S-nucleophiles.

关 键 词：PIPERAZINES DEFLUORINATION DABCO Elimination ENONES PEROXIDES 

分 类 号：O62[理学—有机化学]