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Updated: Feb 11, 2026

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
Published on: April 15, 2013
Radical-Mediated Reactions of α-Bromo Aluminium Thioacetals, α-Bromothioesters, and Xanthates for Thiolactone
Ruairí O McCourt1, Fabrice Dénès2, Eoin M Scanlan3
1School of Chemistry, Trinity Biomedical Sciences Institute (TBSI), Trinity College Dublin, The University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland. mccourro@tcd.ie.
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.
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