酚类衍生物作为芳基自由基前体参与的高选择性反应进展

引用本文: 曹中艳, 金胜男, 王玉霞, 陈依漪, 孔宪强, 徐元清. 酚类衍生物作为芳基自由基前体参与的高选择性反应进展[J]. 大学化学, 2025, 40(4): 245-252. doi: 10.12461/PKU.DXHX202405186 shu

Citation: Zhongyan Cao, Shengnan Jin, Yuxia Wang, Yiyi Chen, Xianqiang Kong, Yuanqing Xu. Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors[J]. University Chemistry, 2025, 40(4): 245-252. doi: 10.12461/PKU.DXHX202405186 shu

酚类衍生物作为芳基自由基前体参与的高选择性反应进展

1.
河南大学化学与分子科学学院, 河南开封 475004;
2.
常州工学院化工与材料学院, 江苏常州 213032
基金项目:
国家自然科学基金(22201062, 22372015, 22202021)；河南大学校级教改项目(HDXJJG-2022-035)

摘要: 酚是年产超千万吨的廉价化工原料，广泛应用于有机合成中的各类重要转化。大学基础化学中关于酚类化合物反应类型的介绍主要是富电子芳环和酚羟基氧上的取代反应，两类产物中均保留了酚的惰性C―O键。为进一步拓展酚类化合物的应用价值，人们通过在酚氧原子上引入不同活化基，借助金属催化打断C―O键，实现了各类高效的脱氧偶联反应。然而，该策略的反应条件通常较为苛刻，并且可能导致产物中有金属残留，限制了其在制药等领域的广泛应用。为挑战上述难题，化学家们发现利用光、电等手段，在温和条件下可将酚的一些简单衍生物通过C―O键的选择性断裂产生芳基自由基。借助芳基自由基的高反应活性和选择性，实现一些新颖和高效的化学转化，为酚的合成应用提供新的策略和方法。本文介绍了利用酚的三氟甲基磺酸酯、磷酸酯和碳酸酯等作为芳基自由基前体的挑战和难点，以及如何实现一些精细化学品精准构建的最新研究进展，期望可以为学有余力的同学们拓宽知识面。

关键词:

English

Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors

1.
College of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004 China;
2.
School of Chemical Engineering and Materials, Changzhou Institute of Technology, Changzhou 213032 China
Received Date: 09 May 2024
Revised Date: 01 August 2024
Available Online: 13 September 2024

Abstract: Phenols, produced at an annual volume exceeding ten million tons, are widely used in various key organic transformations due to their low cost. In introductory chemistry courses, the reactions of phenols typically involve substitutions at the electron-rich aromatic ring or the hydroxyl oxygen, leaving the inert C―O bond intact in the final products. To expand the utility of phenols, researchers have developed metal-catalyzed strategies that cleave the C―O bond by introducing activating groups at the oxygen atom, enabling efficient deoxygenative coupling reactions. However, these methods often require harsh conditions and may result in metal contamination, limiting their use in pharmaceutical and other sensitive applications. To address these limitations, recent studies have demonstrated that simple phenol derivatives can selectively cleave the inert C―O bond under mild conditions, using light or electricity to generate aryl radicals. The high reactivity and selectivity of these radicals enable novel and efficient chemical transformations, offering new strategies for the application of phenols in organic synthesis. This paper reviews recent advancements in using trifluoromethanesulfonates, phosphates, and carbonates of phenols as aryl radical precursors, discussing the challenges and breakthroughs in constructing complex molecules with high precision. This review aims to broaden the knowledge of advanced students in the field.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

酚类衍生物作为芳基自由基前体参与的高选择性反应进展

English

Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

酚类衍生物作为芳基自由基前体参与的高选择性反应进展

English

Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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