期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 76, 期 21, 页码 8999-9007出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo2017444
关键词
-
资金
- Ministry of Education [MOE2010-T2-083]
- Singapore Peking Oxford Research Enterprise (SPORE)
- Science and Technology Plan of Zhejiang Province [2011C24004]
- Singapore-MIT alliance
- National University of Singapore [C-143-000-022]
- KAUST
We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C H bond activation in the presence of stoichiometric CuI, 2,2'-bipyridine and Na2CO3. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2'-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including beta-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and sigma-bond metathesis.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据