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

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

Research output: Contribution to journalArticle

102 Scopus citations

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 Me 2 SiCp 2 'Th[CH 2 (TMS)] 2 (1a; Cp' =n 5 -Me 4 C 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 (US)
Pages (from-to)2062-2063
Number of pages2
JournalJournal of the American Chemical Society
Volume131
Issue number6
DOIs
StatePublished - Feb 18 2009

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'Organoactinide-mediated hydrothiolation of terminal alkynes with aliphatic, aromatic, and benzylic thiols'. Together they form a unique fingerprint.

Cite this