Elusive Thiyl Radical Migration in a Visible Light Induced Chemoselective Rearrangement of gamma-Keto Acrylate Thioesters: Synthesis of Substituted Butenolides

作者：Naskar Sandip; Das Indrajit

来源：Advanced Synthesis & Catalysis, 2017, 359(5): 875-885.

DOI：10.1002/adsc.201601016

<jats:title>Abstract</jats:title><jats:p>The first metal/photocatalyst‐free, visible light induced chemoselective rearrangement of γ‐keto acrylate thioesters via elusive thiyl radical migration is described. Thioesters bearing at least one alkyl substitution undergo 1,2‐thiyl radical migration, whereas 1,4‐migration has been observed when the substrate is substituted by aromatics only. The reactions show excellent functional group tolerance and are proposed to proceed through the <jats:italic>trans‐cis</jats:italic> isomerization/intramolecular lactonization/thiyl radical capture pathway. This atom‐economical process constitutes an efficient and practical method for the formation of substituted butenolides.</jats:p><jats:p><jats:boxed-text content-type="graphic" position="anchor"><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" mimetype="image/png" position="anchor" specific-use="enlarged-web-image" xlink:href="graphic/adsc201601016-toc-0001-m.png"><jats:alt-text>magnified image</jats:alt-text></jats:graphic></jats:boxed-text>
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• 出版日期2017-3-6