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Homogeneous nickel catalysts for the selective transfer of a single arylthio group in the catalytic hydrothiolation of alkynes

(2006) ORGANOMETALLICS. 25(19). p.4462-4470
Author
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

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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.
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.
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.
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.
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://dx.doi.org/10.1021/om060302v},
  volume       = {25},
  year         = {2006},
}

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