1. DFT study on the mechanism of Pd(OAc)-catalyzed hydrothiolation of alkenes bearing heteroatoms with benzenethiol.
- Author
-
Ji, Cai-Hong and Zhang, Xing-Hui
- Subjects
- *
DENSITY functional theory , *REGIOSELECTIVITY (Chemistry) , *MARKOVNIKOV'S rule , *ALKENES , *THIOPHENOL - Abstract
The work reports the theoretical investigation of the mechanism and regioselectivity of the Pd(OAc)-catalyzed hydrothiolation of heteroatom-substituted alkenes with benzenethiol leading to Markovnikov-type product. The reaction process includes: (1) activation of the S-H bond for benzenethiol by the catalyst Pd(OAc); (2) migratory insertion of the alkenes bearing heteroatoms into the Pd-S bond; (3) AcOH molecule attacks Pd-C bonds to give the product and release the catalyst. In addition, the computed results shown that Pd(OAc)-catalyzed hydrothiolation take place by two possible channels and get anti-Markovnikov-type or Markovnikov-type species. The Markovnikov-type reaction channel is more favored with the energy barriers of 21.9-25.6 versus 28.5-31.2 kcal/mol for the anti-Markovnikov-type pathway. The theoretical results and the experimental observations of Tamai and co-workers are consistent. This reaction would proceed in mild conditions and afford the Markovnikov-type products in high yields and regioselectivity. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF