Homogeneous nickel catalysts for the selective transfer of a single arylthio group in the catalytic hydrothiolation of alkynes
- Author
- Denis A Malyshev, Natalie M Scott, Nicolas Marion, Edwin D Stevens, Valentine P Ananikov, Irina P Beletskaya and Steven Nolan (UGent)
- Organization
- Abstract
- A novel homogeneous catalytic system has been developed for the regioselective hydrothiolation of alkynes based on CpNi(NHC)Cl complexes (NHC = N-heterocyclic carbene). The designed catalyst was efficient for the selective addition of a single ArS group to an alkyne and was suitable for the synthesis of vinylsulfides, without side reactions leading to bis(arylthio) alkenes. Furthermore, this catalytic system allowed for the S-H bond addition to alkynes to be performed with high regioselectivity (up to 31:1) and in good yields (61-87%). A mechanistic study showed that this reaction involved three steps: (1) a nickel-based substitution of chloride for the ArS group, (2) alkyne insertion into the Ni-S bond, and (3) protonolysis of the Ni-C bond. The intermediate CpNi(NHC)(SAr) complexes were unambiguously characterized by X-ray analysis.
- Keywords
- OLEFIN METATHESIS CATALYSTS, N-HETEROCYCLIC CARBENES, CARBON-SULFUR BOND, VINYL SULFIDES, RADICAL-ADDITION, REGIOSELECTIVE ADDITION, COMPLEXES BEARING, THIOLS, ACETYLENES, LIGANDS
Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-8169904
- MLA
- Malyshev, Denis A., et al. “Homogeneous Nickel Catalysts for the Selective Transfer of a Single Arylthio Group in the Catalytic Hydrothiolation of Alkynes.” ORGANOMETALLICS, vol. 25, no. 19, 2006, pp. 4462–70, doi:10.1021/om060302v.
- APA
- Malyshev, D. A., Scott, N. M., Marion, N., Stevens, E. D., Ananikov, V. P., Beletskaya, I. P., & Nolan, S. (2006). Homogeneous nickel catalysts for the selective transfer of a single arylthio group in the catalytic hydrothiolation of alkynes. ORGANOMETALLICS, 25(19), 4462–4470. https://doi.org/10.1021/om060302v
- Chicago author-date
- Malyshev, Denis A, Natalie M Scott, Nicolas Marion, Edwin D Stevens, Valentine P Ananikov, Irina P Beletskaya, and Steven Nolan. 2006. “Homogeneous Nickel Catalysts for the Selective Transfer of a Single Arylthio Group in the Catalytic Hydrothiolation of Alkynes.” ORGANOMETALLICS 25 (19): 4462–70. https://doi.org/10.1021/om060302v.
- Chicago author-date (all authors)
- Malyshev, Denis A, Natalie M Scott, Nicolas Marion, Edwin D Stevens, Valentine P Ananikov, Irina P Beletskaya, and Steven Nolan. 2006. “Homogeneous Nickel Catalysts for the Selective Transfer of a Single Arylthio Group in the Catalytic Hydrothiolation of Alkynes.” ORGANOMETALLICS 25 (19): 4462–4470. doi:10.1021/om060302v.
- Vancouver
- 1.Malyshev DA, Scott NM, Marion N, Stevens ED, Ananikov VP, Beletskaya IP, et al. Homogeneous nickel catalysts for the selective transfer of a single arylthio group in the catalytic hydrothiolation of alkynes. ORGANOMETALLICS. 2006;25(19):4462–70.
- IEEE
- [1]D. A. Malyshev et al., “Homogeneous nickel catalysts for the selective transfer of a single arylthio group in the catalytic hydrothiolation of alkynes,” ORGANOMETALLICS, vol. 25, no. 19, pp. 4462–4470, 2006.
@article{8169904,
abstract = {{A novel homogeneous catalytic system has been developed for the regioselective hydrothiolation of alkynes based on CpNi(NHC)Cl complexes (NHC = N-heterocyclic carbene). The designed catalyst was efficient for the selective addition of a single ArS group to an alkyne and was suitable for the synthesis of vinylsulfides, without side reactions leading to bis(arylthio) alkenes. Furthermore, this catalytic system allowed for the S-H bond addition to alkynes to be performed with high regioselectivity (up to 31:1) and in good yields (61-87%). A mechanistic study showed that this reaction involved three steps: (1) a nickel-based substitution of chloride for the ArS group, (2) alkyne insertion into the Ni-S bond, and (3) protonolysis of the Ni-C bond. The intermediate CpNi(NHC)(SAr) complexes were unambiguously characterized by X-ray analysis.}},
author = {{Malyshev, Denis A and Scott, Natalie M and Marion, Nicolas and Stevens, Edwin D and Ananikov, Valentine P and Beletskaya, Irina P and Nolan, Steven}},
issn = {{0276-7333}},
journal = {{ORGANOMETALLICS}},
keywords = {{OLEFIN METATHESIS CATALYSTS,N-HETEROCYCLIC CARBENES,CARBON-SULFUR BOND,VINYL SULFIDES,RADICAL-ADDITION,REGIOSELECTIVE ADDITION,COMPLEXES BEARING,THIOLS,ACETYLENES,LIGANDS}},
language = {{eng}},
number = {{19}},
pages = {{4462--4470}},
title = {{Homogeneous nickel catalysts for the selective transfer of a single arylthio group in the catalytic hydrothiolation of alkynes}},
url = {{http://doi.org/10.1021/om060302v}},
volume = {{25}},
year = {{2006}},
}
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