苯硫基烯酮与不活泼烯烃的分子内[2+2]环加成反应  

Intramolecular[2+2]cycloadditions of Alkyl(Phenylthio)ketenes with unactivated alkenes

作　　者：吴祥 何浩[1,2] 汪涛 邓威力 李有桂[1,2] WU Xiang;HE Hao;WANG Tao;DENG Weili;LI Yougui(School of Chemistry and Chemical Engineering,Hefei University of Technology,Hefei 230009,China;Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering,Hefei University of Technology,Hefei 230009,China;College of Life Sciences,Fujian Normal University,Fuzhou 350117,China)

机构地区：[1]合肥工业大学化学与化工学院,安徽合肥230009 [2]合肥工业大学先进催化材料与反应工程安徽省重点实验室,安徽合肥230009 [3]福建师范大学生命科学学院,福建福州350117

出　　处：《合肥工业大学学报（自然科学版）》2022年第7期984-988,共5页Journal of Hefei University of Technology：Natural Science

基　　金：安徽省重点研究与开发计划资助项目(202104e11020007);中央高校基本科研业务费专项资金资助项目(PA2021GDSK0068)。

摘　　要：为得到具有重要合成价值的多环环丁酮化合物,文章采用2-氯-1-甲基吡啶碘盐(Mukaiyama试剂)处理α-苯硫基羧酸得到α-苯硫基烯酮中间体,使其与不活泼的烯烃进行分子内[2+2]环加成反应,以20%~70%的产率得到多环环丁酮。同时研究发现,当连接烯酮和烯烃的碳链长度以及烯烃的取代受到限制时,[2+2]环加成反应不能发生,α-苯硫基烯酮会发生二聚并转化为还原二聚体和烯胺酮。To obtain a polycyclic cyclobutanone compound having an important synthetic value,2-chloro-1-methylpyridinium iodide(Mukaiyama reagent)was used to obtain anα-(phenylthio)ketenes intermediate.Then,it reacted with unactivated alkenes to undergo intramolecular[2+2]cycloaddition,and polycyclic cyclobutanone was obtained in 20%-70%yield.The study finds that when the tether and the substitution of the alkene are limited,the[2+2]cycloaddition reaction does not occur,andα-(phenylthio)ketenes are dimerized and transformed to reductive dimmers and enaminone.

关 键 词：Mukaiyama试剂 α-苯硫基羧酸 烯酮 [2+2]环加成 环丁酮 还原二聚体 烯胺酮 

分 类 号：O621.3[理学—有机化学]