Hu Weiming, Wang Xilong, Peng Yan, Luo Shuang, Zhao Jiaji, Zhu Qiang
State Key Laboratory of Respiratory Disease, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530, China.
University of Chinese Academy of Sciences, No. 19(A) Yuquan Road, Shijingshan District, Beijing 100049, China.
Org Lett. 2022 May 27;24(20):3642-3646. doi: 10.1021/acs.orglett.2c01217. Epub 2022 May 13.
A chiral phosphoric acid-catalyzed thio-Michael addition/enantioselective protonation has been developed for the first time. The reaction applies 7-methylene-6-aryl-7-dibenzo[]azepines, products of Pd-catalyzed imidoylative Heck cyclization, as Michael acceptors in reactions with a wide range of aryl thiols. Diversified 7-[(arylthio)methyl]-7-dibenzo[]azepines bearing a benzylic stereocenter and a thermodynamically regulated biaryl axis were produced with good to excellent enantioselectivity and 14-25:1 diastereoisomeric ratios.
首次开发了一种手性磷酸催化的硫代迈克尔加成/对映选择性质子化反应。该反应使用钯催化的亚氨基 Heck 环化产物 7-亚甲基-6-芳基-7-二苯并[]氮杂卓作为迈克尔受体，与多种芳基硫醇发生反应。生成了具有苄基立体中心和热力学调控的联芳基轴的多种 7-[(芳硫基)甲基]-7-二苯并[]氮杂卓，对映选择性良好至优异，非对映异构体比例为 14-25:1。
