Ex Situ Formation of Methanethiol: Application in the Gold(I)-Promoted Anti-Markovnikov Hydrothiolation of Olefins

Steffan K. Kristensen; Simon L.R. Laursen; Esben Taarning; Troels Skrydstrup

doi:10.1002/anie.201809051

Ex Situ Formation of Methanethiol: Application in the Gold(I)-Promoted Anti-Markovnikov Hydrothiolation of Olefins

Steffan K. Kristensen, Simon L.R. Laursen, Esben Taarning, Troels Skrydstrup^*

^*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

47 Citations (Scopus)

Abstract

A protocol for the Au-promoted anti-Markovnikov hydrothiolation of olefins using ex situ generated methanethiol is reported. The use of S-methylisothiourea hemisulfate salt as a solid precursor for methanethiol generation ensures a safe and reliable deliverance of a stoichiometric amount of this thiol. The procedure was shown to work for a broad range of olefins providing the corresponding hydrothiolated adduct in good to excellent yields. Mechanistic evaluations suggest that thiyl radicals are generated and that gold acts as an efficient but stable radical initiator.

Original language	English
Journal	Angewandte Chemie - International Edition
Volume	57
Issue	42
Pages (from-to)	13887-13891
Number of pages	5
ISSN	1433-7851
DOIs	https://doi.org/10.1002/anie.201809051
Publication status	Published - 1 Jan 2018

Keywords

gold
hydrothiolation
radical pathway
reaction mechanisms
thioethers

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title = "Ex Situ Formation of Methanethiol: Application in the Gold(I)-Promoted Anti-Markovnikov Hydrothiolation of Olefins",

abstract = "A protocol for the Au-promoted anti-Markovnikov hydrothiolation of olefins using ex situ generated methanethiol is reported. The use of S-methylisothiourea hemisulfate salt as a solid precursor for methanethiol generation ensures a safe and reliable deliverance of a stoichiometric amount of this thiol. The procedure was shown to work for a broad range of olefins providing the corresponding hydrothiolated adduct in good to excellent yields. Mechanistic evaluations suggest that thiyl radicals are generated and that gold acts as an efficient but stable radical initiator.",

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Ex Situ Formation of Methanethiol: Application in the Gold(I)-Promoted Anti-Markovnikov Hydrothiolation of Olefins. / Kristensen, Steffan K.; Laursen, Simon L.R.; Taarning, Esben et al.
In: Angewandte Chemie - International Edition, Vol. 57, No. 42, 01.01.2018, p. 13887-13891.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

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T2 - Application in the Gold(I)-Promoted Anti-Markovnikov Hydrothiolation of Olefins

AU - Kristensen, Steffan K.

AU - Laursen, Simon L.R.

AU - Taarning, Esben

AU - Skrydstrup, Troels

PY - 2018/1/1

Y1 - 2018/1/1

N2 - A protocol for the Au-promoted anti-Markovnikov hydrothiolation of olefins using ex situ generated methanethiol is reported. The use of S-methylisothiourea hemisulfate salt as a solid precursor for methanethiol generation ensures a safe and reliable deliverance of a stoichiometric amount of this thiol. The procedure was shown to work for a broad range of olefins providing the corresponding hydrothiolated adduct in good to excellent yields. Mechanistic evaluations suggest that thiyl radicals are generated and that gold acts as an efficient but stable radical initiator.

AB - A protocol for the Au-promoted anti-Markovnikov hydrothiolation of olefins using ex situ generated methanethiol is reported. The use of S-methylisothiourea hemisulfate salt as a solid precursor for methanethiol generation ensures a safe and reliable deliverance of a stoichiometric amount of this thiol. The procedure was shown to work for a broad range of olefins providing the corresponding hydrothiolated adduct in good to excellent yields. Mechanistic evaluations suggest that thiyl radicals are generated and that gold acts as an efficient but stable radical initiator.

KW - gold

KW - hydrothiolation

KW - radical pathway

KW - reaction mechanisms

KW - thioethers

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U2 - 10.1002/anie.201809051

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VL - 57

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JO - Angewandte Chemie - International Edition

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IS - 42

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Ex Situ Formation of Methanethiol: Application in the Gold(I)-Promoted Anti-Markovnikov Hydrothiolation of Olefins

Abstract

Keywords

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