Molecules 2018, 23(4), 897; https://doi.org/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
▼
Figures
Scheme 1
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).
Share & Cite This Article
MDPI and ACS Style
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.
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.
Related Articles
Article Metrics
Comments
[Return to top]
Molecules
EISSN 1420-3049
Published by MDPI AG, Basel, Switzerland
RSS
E-Mail Table of Contents Alert