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.
