Computational and Experimental Studies of Phthaloyl Peroxide-Mediated Hydroxylation of Arenes Yield a More Reactive Derivative, 4,5-Dichlorophthaloyl Peroxide
Computational and Experimental Studies of Phthaloyl Peroxide-Mediated Hydroxylation of Arenes Yield a More Reactive Derivative, 4,5-Dichlorophthaloyl Peroxide
复制标题
DOI：
10.1021/acs.joc.5b01079
复制
发表时间：
2015-08-21
影响因子：
3.6
通讯作者：
Siegel, Dionicio
中科院分区：
文献类型：
--
作者：
Camelio, Andrew M.;Liang, Yong;Siegel, Dionicio
邻苯二甲酰过氧化氢氧化芳烃为酚类化合物的合成提供了一种新的方法。一种新的，更具反应性的芳烃氧化剂，4，5-二氯邻苯二甲酰过氧化物，计算预测和实验确定具有增强的反应性，扩大了反应的范围，同时保持了高水平的耐受性不同的官能团。该反应通过一种新的“反向反弹”机制与双自由基中间体进行。通过分离和表征次要副产物，线性自由能相关性的测定，和芳烃的取代基效应的计算分析，实现了机制的洞察力，其中每一个都提供了额外的支持，通过双自由基途径进行反应。
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 "reverse-rebound" 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.