Nucleophilic Deoxyfluorination of Phenols via Aryl Fluorosulfonate Intermediates

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• 作者：Sydonie D. Schimler ; Megan A. Cismesia ; Patrick S. Hanley ; Robert D. J. Froese ; Matthew J. Jansma ; Douglas C. Bland ; Melanie S. Sanford
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：February 1, 2017
• 年：2017
• 卷：139
• 期：4
• 页码：1452-1455
• 全文大小：386K
• ISSN：1520-5126

文摘

This report describes a method for the deoxyfluorination of phenols with sulfuryl fluoride (SO₂F₂) and tetramethylammonium fluoride (NMe₄F) via aryl fluorosulfonate (ArOFs) intermediates. We first demonstrate that the reaction of ArOFs with NMe₄F proceeds under mild conditions (often at room temperature) to afford a broad range of electronically diverse and functional group-rich aryl fluoride products. This transformation was then translated to a one-pot conversion of phenols to aryl fluorides using the combination of SO₂F₂ and NMe₄F. Ab initio calculations suggest that carbon–fluorine bond formation proceeds via a concerted transition state rather than a discrete Meisenheimer intermediate.