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

被引：43
作者：
Kristensen, Steffan K. [1 ,2 ]
Laursen, Simon L. R. [1 ,2 ]
Taarning, Esben [3 ]
Skrydstrup, Troels [1 ,2 ]
机构：
[1] Aarhus Univ, Carbon Dioxide Activat Ctr CADIAC, Dept Chem, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark
[2] Aarhus Univ, Interdisciplinary Nanosci Ctr iNANO, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark
[3] Haldor Topsoe Res Labs, Sustainable Chem R&D, Haldor Topsoes Alle 1, DK-2800 Lyngby, Denmark
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 42期
基金：
新加坡国家研究基金会;
关键词：
gold; hydrothiolation; radical pathway; reaction mechanisms; thioethers; SULFENYLATED CARBONYL-COMPOUNDS; VINYL SULFIDES; PROPARGYLIC ALCOHOLS; CATALYZED ADDITION; C-S; 2-CHAMBER REACTORS; GOLD CATALYSIS; BOND FORMATION; THIOLS; EFFICIENT;
D O I：
10.1002/anie.201809051
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A protocol for the Au-promoted anti-Markovnikov hydrothiolation of olefins using exsitu 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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收藏
页码：13887 / 13891
页数：5
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