Phase-transfer-shuttle generated in situ enables novel SN1-type fluorination of sulfonium ylide with hydrofluoric acid  

作　　者：Yisa Xiao Rui Wang Zhaoxuan Xu Qunchao Zhao Renyi Pang Tao Dong Long Lu Qilong Shen 

机构地区：[1]Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials,Shanghai Institute of Organic Chemistry,University of Chinese Academy Sciences,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Science China Chemistry》2025年第2期641-648,共8页中国科学(化学英文版)

基　　金：supported by the National Key Research and Development Program of China(Grant Number 2021YFF0701-700);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0590000).

摘　　要：The development of a nucleophilic fluorination protocol using hydrofluoric acid as the fluoride source represents a long-sought goal in the field of organofluorine chemistry.We report herein the realization of such a reaction that employed alkyl-substituted sulfonium ylides as the substrates.The key to the success of the protocol was attributed to two factors:First,as a Brϕnsted base,the ylide was able to be protonated by HFaq,thus serving as a phase-transfer shuttle generated in situ to bring F−from aqueous phase to the organic phase promoting desolvation of fluoride ion.Second,after protonation,a sulfonium salt,a good leaving group,was generated and subsequent attacked by the fluoride to afford the alkyl fluoride.Mechanistic investigation indicates that the reaction occurs via an SN1 pathway.Because of the nature of the cationic intermediate in the reaction,two attractive rearrangement-fluorination approaches including 1,2-aryl migration fluorination and ring-expansion fluorination were disclosed.

关 键 词：SN1 FLUORINATION hydrofluoric acid sulfonium ylide cation rearrangement 

分 类 号：O64[理学—物理化学]