Department of Applied Chemistry, School of Science, Anhui Agricultural University, Hefei 230036, P. R. China.
J Org Chem. 2022 Jun 17;87(12):7895-7904. doi: 10.1021/acs.joc.2c00545. Epub 2022 Jun 6.
A facile and general method for palladium-catalyzed stereoselective bisthiolation of terminal alkynes with allyl phenyl sulfides has been developed. The scope and versatility of the reaction have been demonstrated, and a broad range of substrates bearing electron-donating and -withdrawing groups on the aromatic rings were all compatible with this reaction, providing the desired ()-1,2-dithio-1-alkenes in moderate to good yields. Preliminary mechanistic studies demonstrated that the sulfur source of the desired products may be successively incorporated into alkynes via C-S bond cleavage of two molecules of allyl phenyl sulfides and ruled out the possibility of vinyl sulfides, alkynyl sulfides, and disulfide intermediates being involved in this reaction.
一种简便、通用的钯催化末端炔烃与烯丙基苯硫醚的立体选择性双硫代反应方法已经被开发出来。该反应的适用范围和多功能性已经得到了证明，并且具有给电子和吸电子取代基的广泛的芳环取代底物都与该反应相容，以中等至良好的收率提供所需的 ()-1,2-二硫-1-烯烃。初步的机理研究表明，所需产物的硫源可能通过两个烯丙基苯硫醚分子的 C-S 键断裂连续掺入到炔烃中，排除了乙烯基硫醚、炔基硫醚和二硫代中间体参与该反应的可能性。
