Preparative Scale Demonstration and Mechanistic Investigation of a Visible Light-Mediated Radical Smiles Rearrangement

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• 作者：James J. Douglas ; Martin J. Sevrin ; Kevin P. Cole ; Corey R. J. Stephenson
• 刊名：Organic Process Research & Development
• 出版年：2016
• 出版时间：July 15, 2016
• 年：2016
• 卷：20
• 期：7
• 页码：1148-1155
• 全文大小：465K
• 年卷期：0
• ISSN：1520-586X

文摘

A visible light-mediated Smiles rearrangement providing the difluoroethanol motif has been shown to reliably operate on preparative scale up to 100 g of starting material. Mechanistic investigation has revealed the reaction proceeds predominantly via a radical chain process that in some instances can be initiated via visible light or thermal activation in the absence of a photocatalyst. The reaction was demonstrated in continuous flow, with visible light and thermal initiation using a thiophene substrate relevant to pharmaceutical development.