%0 Journal Article %A Ranjit, Sadananda %A Lee, Richmond %A Heryadi, Dodi %A Shen, Chao %A Wu, Ji’En %A Zhang, Pengfei %A Huang, Kuo-Wei %A Liu, Xiaogang %D 2016 %T Copper-Mediated C–H Activation/C–S Cross-Coupling of Heterocycles with Thiols %U https://acs.figshare.com/articles/journal_contribution/Copper_Mediated_C_H_Activation_C_S_Cross_Coupling_of_Heterocycles_with_Thiols/2589676 %R 10.1021/jo2017444.s001 %2 https://acs.figshare.com/ndownloader/files/4236469 %K alkyl thiols %K aryl %K thiolation reactions %K bond %K hydrogen atom abstraction pathway %K indole substrates %K electron transfer %K reaction mechanism %K bipyridine %K stoichiometric CuI %K ThiolsWe report %K elimination %K Na 2CO %K bidentate ligand %K alkyl group %K hydrogen atom transfer %X 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 β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis. %I ACS Publications