Molecules 2018, 23(4), 897; doi:10.3390/molecules23040897
Radical-Mediated Reactions of α-Bromo Aluminium Thioacetals, α-Bromothioesters, and Xanthates for Thiolactone Synthesis
1
School of Chemistry, Trinity Biomedical Sciences Institute (TBSI), Trinity College Dublin, The University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland
2
CEISAM UMR CNRS 6230, Université de Nantes, UFR des Sciences et des Techniques, 2 rue de la Houssinière, BP 92208, 44322 Nantes CEDEX 3, France
*
Author to whom correspondence should be addressed.
Academic Editors: John C. Walton and Derek J. McPhee
Received: 9 March 2018 / Revised: 3 April 2018 / Accepted: 10 April 2018 / Published: 13 April 2018
(This article belongs to the Special Issue Radical Chemistry)
Abstract
Thiolactones have attracted considerable attention in recent years as bioactive natural products, lead compounds for drug discovery, molecular probes, and reagents for polymerisation. We have investigated radical-mediated C-C bond forming reactions as a strategy for thiolactone synthesis. Cyclisation of an α-bromo aluminium thioacetal was investigated under radical conditions. It was found that at low temperature, a radical fragmentation and rearrangement process occurs. A putative reaction mechanism involving a previously unreported aluminium templated thiol-ene step for the rearrangement process is presented. Cyclisation reactions of α-bromo thioesters and α-xanthate thioesters under radical mediated conditions furnished the desired thiolactones in moderate yields. View Full-TextKeywords:
radical fragmentation; radical cyclisation; thiyl radical
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McCourt, R.O.; Dénès, F.; Scanlan, E.M. Radical-Mediated Reactions of α-Bromo Aluminium Thioacetals, α-Bromothioesters, and Xanthates for Thiolactone Synthesis. Molecules 2018, 23, 897.
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