Gold-Catalyzed Proto- and Deuterodeboronation

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• 作者：Graeme Barker ; Stacey Webster ; David G. Johnson ; Rachel Curley ; Matthew Andrews ; Paul C. Young ; Stuart A. Macgregor ; Ai-Lan Lee
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：October 16, 2015
• 年：2015
• 卷：80
• 期：20
• 页码：9807-9816
• 全文大小：610K
• ISSN：1520-6904

文摘

A mild gold-catalyzed protodeboronation reaction, which does not require acid or base additives and can be carried out in 鈥済reen鈥?solvents, is described. As a result, the reaction is very functional-group-tolerant, even to acid- and base-sensitive functional groups, and should allow for the boronic acid group to be used as an effective traceless directing or blocking group. The reaction has also been extended to deuterodeboronations for regiospecific ipso-deuterations of aryls and heteroaryls from the corresponding organoboronic acid. Based on density functional theory calculations, a mechanism is proposed that involves nucleophilic attack of water at boron followed by rate-limiting B鈥揅 bond cleavage and facile protonolysis of a Au鈭捪?phenyl intermediate.