Organoactinide-mediated hydrothiolation of terminal alkynes with aliphatic, aromatic, and benzylic thiols

Charles J. Weiss, Stephen D. Wobser, Tobin J. Marks

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98 Citations (Scopus)

Abstract

Atom-efficient organoactinide-catalyzed intermolecular hydrothiolation of terminal alkynes is achieved by Th(IV) and U(IV) complexes to yield vinyl sulfides. The conversion is highly Markovnikov selective and is capable of utilizing aromatic, benzylic, and aliphatic thiols. Kinetic measurements of the transformation mediated by Me2SiCp2'Th[CH 2(TMS)]2 (1a; Cp' =n5-Me4C 5) shows the reaction is zero-order in [thiol], first-order in [1a], first-order in [alkyne] at lower alkyne concentrations, and zero-order at higher [alkyne]. The proposed catalytic cycle invokes turnover-limiting insertion of the alkyne into the Th-S bond followed by a rapid Th-C bond protonolysis. All reactions except entries 7 and 8 are quantitative by 1H NMR.

Original languageEnglish
Pages (from-to)2062-2063
Number of pages2
JournalJournal of the American Chemical Society
Volume131
Issue number6
DOIs
Publication statusPublished - Feb 18 2009

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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