银催化炔酮的自由基烷基化/5-endo环化反应研究  

Sliver catalyzed radical alkylation/5-endo annulation of ynones

作　　者：王庆归 郑汉良 朱钢国[1] WANG Qinggui;ZHENG Hanliang;ZHU Gangguo(College of Chemistry and Materials Sciences,Zhejiang Normal University,Jinhua 321004,China)

机构地区：[1]浙江师范大学化学与材料科学学院,浙江金华321004

出　　处：《浙江师范大学学报（自然科学版）》2023年第4期402-407,共6页Journal of Zhejiang Normal University:Natural Sciences

基　　金：国家自然科学基金资助项目(22071218);浙江省自然科学基金资助项目(LZ20B020001;LY20B020006)。

摘　　要：为了通过炔酮高效合成环戊酮衍生物,开发了一个银催化炔酮的自由基烷基化/5-endo环化反应.反应以芳基炔酮和烷基羧酸为原料,通过烷基羧酸氧化脱羧产生烷基自由基、自由基对炔酮加成、1,5-氢迁移、5-endo环化、分子间氢迁移或还原质子化等步骤,高非对映选择性地构建了α-烷基环戊酮衍生物.结果表明:该环化反应的效率较高,产率最高可达83%;反应的官能团兼容性良好,适用于多种炔酮与烷基羧酸.此环化反应的发展为复杂多取代环戊酮衍生物的高效构筑提供了新思路.In order to construct cyclopentanone derivatives from ynones,a sliver catalyzed radical alkylation/5-endo annulation of ynones was developed.Using alkyl carboxylic acids as the radical precursor,the reaction proceeded via decarboxylation of alkyl carboxylic acid,regioselective radical addition to ynones,1,5-hydrogen atom transfer(1,5-HAT),5-endo annulation,and intramolecular HAT or reductive protonation to afford theα-alkylated cyclopentanones in a highly diastereoselective way.The results indicated that the reaction possessed high efficiency and good functional group compatibility,moderate to good yields could be achieved for reactions of various aryl ynones and carboxylic acids.This reaction offered a promising method for the efficient construction of densely functionalized cyclopentanones.

关 键 词：炔酮 自由基 环戊酮 1 5-氢迁移 5-endo环化 

分 类 号：O621.3[理学—有机化学]