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Ex Situ Formation of Methanethiol: Application in the Gold(I)‐Promoted Anti‐Markovnikov Hydrothiolation of Olefins
Author(s) -
Kristensen Steffan K.,
Laursen Simon L. R.,
Taarning Esben,
Skrydstrup Troels
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201809051
Subject(s) - methanethiol , markovnikov's rule , chemistry , adduct , thiol , organic chemistry , radical , in situ , combinatorial chemistry , catalysis , medicinal chemistry , regioselectivity , sulfur
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.