原位产生二氧化锰催化构建S-S键  

Highly Active Manganese Dioxide Catalyzed the Construction of S-S Bond

作　　者：吕进强 曾竟 阿布都热西提·阿布力克木 LüJinqiang;Zeng Jing;Abulikemu Abudu Rexit(Department of Chemistry,Xinjiang Normal University,Urumqi 830054)

机构地区：[1]新疆师范大学化学系,乌鲁木齐830054

出　　处：《有机化学》2020年第8期2483-2490,共8页Chinese Journal of Organic Chemistry

基　　金：新疆维吾尔自治区高校科研计划自然科学重点项目(No.XJEDU2020I015);新疆维吾尔自治区2017年自治区“天山青年计划”(No.2017Q026)资助项目.

摘　　要：利用0.1~0.2 equiv.高锰酸钾在无水乙醇体系中原位生成高活性二氧化锰,并以此为催化剂,促使硫酚、硫醇类化合物在室温下发生自由基自身偶联反应构建S—S键,获得了14种对称双硫化物,产率介于70%~99%;同时发现该催化体系还可催化对称双硫化物与不同取代基的硫酚、硫醇或两个不同的对称双硫化物,发生自由基交叉偶联反应合成了13个不对称双硫化合物,产率19%~72%.该法具有简单高效、后处理简单、绿色溶剂、底物适用范围广、条件温和等优点,所有产物均经1H NMR、13C NMR结构确证.Generation of highly active manganese dioxide in situ by using catalytic amount of potassium permanganate in anhydrous ethanol system,the catalytic system promoted S-S bond construction by free radical self coupling reactions of thiophenol and mercaptan compounds at room temperature.14 disulfides were obtained with 70%~99%yields.At the same time,it was also found that the catalytic system could also catalyze radical cross-coupling reactions between symmetric disulfides and different substituents of thiophenols,thiols,or two different symmetric disulfides,13 asymmetric disulfides were obtained with 19%~72%yields.The protocol offered the advantages of simple and efficient,easy separation,green solvent,wide range of substrate applications,and mild conditions.All products were confirmed by 1H NMR and 13C NMR spectra.

关 键 词：自由基偶联反应 S-S键 二氧化锰 

分 类 号：O621.251[理学—有机化学]