Copper Catalyzed sp3 C–H Etherification with Acyl Protected Phenols

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• 作者：Tolani K. Salvador ; Charles H. Arnett ; Subrata KunduNicholas G. Sapiezynski ; Jeffery A. Bertke ; Mahdi Raghibi Boroujeni ; Timothy H. Warren
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：December 28, 2016
• 年：2016
• 卷：138
• 期：51
• 页码：16580-16583
• 全文大小：516K
• ISSN：1520-5126

文摘

A variety of acyl protected phenols AcOAr participate in sp³ C-H etherification of substrates R-H to give alkyl aryl ethers R-OAr employing ^tBuOO^tBu as oxidant with copper(I) β-diketiminato catalysts [Cu^I]. Although 1°, 2°, and 3° C-H bonds may be functionalized, selectivity studies reveal a preference for the construction of hindered, 3° C-OAr bonds. Mechanistic studies indicate that β-diketiminato copper(II) phenolates [Cu^II]-OAr play a key role in this C-O bond forming reaction, formed via transesterification of AcOAr with [Cu^II]-O^tBu intermediates generated upon reaction of [Cu^I] with ^tBuOO^tBu.