Computational and Experimental Studies of Phthaloyl Peroxide-Mediated Hydroxylation of Arenes Yield a More Reactive Derivative, 4,5-Dichlorophthaloyl Peroxide

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• 作者：Andrew M. Camelio ; Yong Liang ; Anders M. Eliasen ; Trevor C. Johnson ; Changxia Yuan ; Alex W. Schuppe ; K. N. Houk ; Dionicio Siegel
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：August 21, 2015
• 年：2015
• 卷：80
• 期：16
• 页码：8084-8095
• 全文大小：535K
• ISSN：1520-6904

文摘

The oxidation of arenes by the reagent phthaloyl peroxide provides a new method for the synthesis of phenols. A new, more reactive arene oxidizing reagent, 4,5-dichlorophthaloyl peroxide, computationally predicted and experimentally determined to possess enhanced reactivity, has expanded the scope of the reaction while maintaining a high level of tolerance for diverse functional groups. The reaction proceeds through a novel 鈥渞everse-rebound鈥?mechanism with diradical intermediates. Mechanistic insight was achieved through isolation and characterization of minor byproducts, determination of linear free energy correlations, and computational analysis of substituent effects of arenes, each of which provided additional support for the reaction proceeding through the diradical pathway.