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

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

doi:10.1021/ja808764q

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

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

Northwestern University

Research output: Contribution to journal › Article

100 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 language	English
Pages (from-to)	2062-2063
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	131
Issue number	6
DOIs	https://doi.org/10.1021/ja808764q
Publication status	Published - Feb 18 2009

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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Weiss, C. J., Wobser, S. D., & Marks, T. J. (2009). Organoactinide-mediated hydrothiolation of terminal alkynes with aliphatic, aromatic, and benzylic thiols. Journal of the American Chemical Society, 131(6), 2062-2063. https://doi.org/10.1021/ja808764q

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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.",

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AU - Weiss, Charles J.

AU - Wobser, Stephen D.

AU - Marks, Tobin J.

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N2 - 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.

AB - 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.

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