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

Denis A. Malyshev, Natalie M. Scott, Nicolas Marion, Edwin D. Stevens, Valentine P. Ananikov, Irina P. Beletskaya, Steven Patrick Nolan

Research output: Contribution to journalArticlepeer-review

155 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)4462-4470
Number of pages9
JournalOrganometallics
Volume25
Issue number19
DOIs
Publication statusPublished - 11 Sept 2006

Keywords

  • OLEFIN METATHESIS CATALYSTS
  • N-HETEROCYCLIC CARBENES
  • CARBON-SULFUR BOND
  • VINYL SULFIDES
  • RADICAL-ADDITION
  • REGIOSELECTIVE ADDITION
  • COMPLEXES BEARING
  • THIOLS
  • ACETYLENES
  • LIGANDS

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