铜催化的降冰片烯硫化反应合成三环[2.2.1.0^(2,6)]庚烷衍生物  

Copper-catalyzed Sulfuration of Norbornene to Synthesize Tricyclo[2.2.1.0^(2,6)]heptane Derivatives

作　　者：刘园 龙鑫 邹胜 白元盛 王庆印 王公应 LIU Yuan;LONG Xin;ZOU Sheng;BAI Yuansheng;WANG Qingyin;WANG Gongying(Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences,Chengdu 610299,China;University of Chinese Academy of Sciences,Beijing 100049,China;Chengdu Organic Chemistry Co.,Ltd.,Chinese Academy of Sciences,Chengdu 610299,China)

机构地区：[1]中国科学院成都有机化学研究所,四川成都610299 [2]中国科学院大学,北京100049 [3]中国科学院成都有机化学有限公司,四川成都610299

出　　处：《合成化学》2025年第3期177-183,共7页Chinese Journal of Synthetic Chemistry

基　　金：中央在川高校院所重大科技成果转化项目(绿色环保铝基聚酯切片关键技术研究及产业化:2022ZHCG0135)。

摘　　要：具有三环[2.2.1.0^(2,6)]庚烷结构单元的天然产物表现出广泛的生物学活性,因此开发合成三环[2.2.1.0^(2,6)]庚烷衍生物的新方法具有重要意义。研究了铜催化的降冰片烯硫化反应,合成了系列苯硫基三环[2.2.1.0^(2,6)]庚烷衍生物。以降冰片烯和二硫醚为原料,碘化亚铜为催化剂,二甲基亚砜(DMSO)为溶剂,150℃空气氛围下反应4 h,最终以66%~96%的产率获得相应产物。其结构经^(1)H NMR,^(13)C NMR和HR-MS进行了确证,并确定了单晶分子结构。该反应具有原料简单易得,催化剂廉价和操作简单等优点。Natural products with tricyclo[2.2.1.0^(2,6)]heptane structural units display a wide range of biological activities.Therefore,it is of great significance to develop new methods for the synthesis of tricyclo[2.2.1.0^(2,6)]heptane derivatives.Herein,copper-catalyzed sulfuration of norbornene was studied and synthesized a series of phenylthiotricyclo[2.2.1.0^(2,6)]heptane derivatives.The corresponding products were finally obtained in the yield of 66%~96%,using norbornene and disulfides as raw materials,CuI as catalyst,dimethyl sulfoxide(DMSO)as the solvent,reacted at 150℃for 4 hours under air.The structures were characterized by^(1)H NMR,^(13)C NMR and HR-MS,and were confirmed by single crystal structures.This reaction has the advantages of using readily available substrates,cheap catalyst and simple operation.

关 键 词：铜催化 降冰片烯 三环[2.2.1.0^(2 6)]庚烷 二硫醚 二甲基亚砜 

分 类 号：O621.3[理学—有机化学] O624[理学—化学]