Institute of Next Generation Matter Transformation, College of Chemical Engineering at, Huaqiao University, 668 Jimei Blvd, Xiamen, Fujian, 361021, P.R. China.
Fujian Provincial Key Laboratory of Biochemical Technology, College of Chemical Engineering at, Huaqiao University, 668 Jimei Blvd, Xiamen, Fujian, 361021, P.R. China.
Angew Chem Int Ed Engl. 2017 Jun 26;56(27):7952-7957. doi: 10.1002/anie.201704091. Epub 2017 Jun 14.
An efficient and convenient synthesis of valuable disulfanes and benzenesulfonothioates, having a 2-aminofuran framework, has been developed by employing a copper-catalyzed transformation of readily available N-tosylhydrazone-bearing thiocarbamates. This method features an inexpensive metal catalyst, mild reaction conditions, good functional-group tolerance, short reaction times, and delivers valuable and complex products. A copper carbene generated from an N-tosylhydrazone-bearing thiocarbamate is proposed as the key intermediate for the transformation and it triggers the subsequent cascade. Remarkably, the Ts anion released from N-tosylhydrazone further serves as a nucleophile, thus rendering the formation of benzenesulfonothioates under controlled conditions.
一种高效、便捷的合成具有 2-氨基呋喃骨架的有价值的二硫烷和苯磺硫酯的方法已经开发出来，该方法采用了铜催化的易于获得的 N-对甲苯磺酰基腙基硫代氨基甲酸酯的转化。该方法具有价格低廉的金属催化剂、温和的反应条件、良好的官能团耐受性、较短的反应时间，并提供有价值和复杂的产物。从 N-对甲苯磺酰基腙基硫代氨基甲酸酯生成的铜卡宾被提出作为转化的关键中间体，并触发了随后的级联反应。值得注意的是，从 N-对甲苯磺酰基腙释放的 Ts 阴离子进一步充当亲核试剂，从而在受控条件下形成苯磺硫酯。
