Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (5): 1658-1666.DOI: 10.6023/cjoc202310035 Previous Articles     Next Articles

ARTICLES

卤化钠促进硫-硅键活化及其在非对称硫醚合成中的应用

梁家仪a, 杨雅淇a, 刘建平a,*(), 徐清a,*(), 韩立彪b,*()   

  1. a 温州大学化学与材料工程学院 苍南研究院 浙江温州 325035
    b 浙江扬帆新材料股份有限公司 浙江上虞 312369
  • 收稿日期:2023-10-31 修回日期:2023-12-11 发布日期:2024-01-11
  • 基金资助:
    浙江省领军创新创业团队引进计划(2022R01021); 国家自然科学基金(21672163)

Sodium Halides-Promoted S—Si Bond Activation and Its Application in the Synthesis of Unsymmetrical Thioethers

Jiayi Lianga, Yaqi Yanga, Jianping Liua(), Qing Xua(), Libiao Hanb()   

  1. a Cangnan Institute, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035
    b Zhejiang Yangfan New Materials Co., Ltd., Shangyu, Zhejiang 312369
  • Received:2023-10-31 Revised:2023-12-11 Published:2024-01-11
  • Contact: *E-mail: qing-xu@wzu.edu.cn; hlb@shoufuchem.com; 518liujianping@163.com
  • Supported by:
    Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2022R01021); National Natural Science Foundation of China(21672163)

Unlike the conventional methods that require the use of fluoride salts for activation of the E—Si bonds of organosilicon compounds by forming the strong Si—F bond, simple inorganic salt NaBr even the table salt NaCl could be used to effectively activate the S—Si bond through formation of the relatively weaker Si—X (X=Br, Cl) bonds. Employing this method, inorganic sodium halides can be used to promote the reaction of thiosilanes with non-fluorine alkyl halides, producing unsymmetrical alkyl thioethers under base-free neutral conditions. The reaction produced silyl halides TMSX as byproduct, which could be recovered. This method could also be extended to non-fluorine heteroaryl halides and electron-deficient aryl halides for the synthesis of heteroaryl and electron-deficient aryl thioethers, revealing the relatively broad substrate scope of the method.

Key words: thiosilanes, S—Si bond activation, sodium halides, unsymmetrical thioethers