(杂)芳烃的电化学碳-氢膦酰化反应研究进展

doi:10.6023/cjoc202506033

摘要/Abstract

膦酰化的(杂)芳烃作为一类重要的有机膦化合物, 在有机催化、药物化学以及材料科学等领域展现出广泛的应用价值. 其中, (杂)芳烃的碳-氢膦酰化反应因其原子经济性和步骤简洁性, 成为构建该类化合物的最有效策略之一. 近年来, 随着有机电化学的快速发展, 电驱动的碳-氢膦酰化反应取得了重要突破. 与传统方法相比, 电化学策略具有如下显著优势: 一方面以电子替代传统化学氧化剂, 提高了反应的原子经济性; 另一方面反应条件温和, 表现出优异的官能团兼容性. 综述了(杂)芳烃电化学碳-氢膦酰化的最新研究进展, 重点阐述了反应机理, 阐明了方法的适用范围. 为便于读者理解, 依据电解模式(直接电解与间接电解), 将所讨论的反应体系划分为两大类.

关键词: 有机电化学, 电氧化, 电催化, 膦酰化, (杂)芳烃

Phosphonylated (hetero)arenes, as an important class of organophosphorus compounds, exhibit broad application value in fields such as organic catalysis, medicinal chemistry, and materials science. Among various synthetic approaches, the C—H phosphonylation of (hetero)arenes stands out as one of the most efficient strategies for synthesizing these compounds due to its atom economy and step simplicity. In recent years, with the rapid development of organic electrochemistry, significant breakthroughs have been achieved in electrochemically driven C—H phosphonylation. Compared with traditional methods, the electrochemical strategy offers distinct advantages: (1) it replaces chemical oxidants with electrons, improving atom economy, and (2) it demonstrates excellent functional group compatibility under mild conditions. This review summarizes the latest advances in the electrochemical C—H phosphonylation of (hetero)arenes, with a focus on reaction mechanisms and substrate scope. For clarity, the discussed reaction systems are categorized into two major classes based on the electrolysis mode (direct electrolysis vs. indirect electrolysis).

Key words: organic electrosynthesis, electrooxidation, electrocatalysis, phosphonylation, (hetero)arenes

引用此文

刘若雨, 梁炳玉, 陈书阳, 孙红先, 孙一冰, 叶勇. (杂)芳烃的电化学碳-氢膦酰化反应研究进展[J]. 有机化学, 2025, 45(12): 4290-4297.

Ruoyu Liu, Bingyu Liang, Shuyang Chen, Hongxian Sun, Yibing Sun, Yong Ye. Recent Advances of C—H Phosphonylation of (Hetero)arenes under Electrochemical Conditions[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4290-4297.

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图/表 10

图式1. 喹喔啉酮的直接电化学膦酰化反应

Scheme 1. Direct electrochemical phosphorylation of quinoxalinones

图式2. N-未保护喹喔啉酮的直接电化学膦酰化反应

Scheme 2. Direct electrochemical phosphorylation of N-unpro- tected quinoxalinones

图式3. 2-苯基咪唑并[1,2-a]吡啶与三烷基亚磷酸酯的电化学脱氢偶联反应

Scheme 3. Electrochemical cross-dehydrogenative coupling of 2-phenylimidazo[1,2-a]pyridines and trialkylphosphites

图式4. 吖啶类化合物的电化学碳-氢膦酰化反应

Scheme 4. Electrochemical C—H phosphorylation of acridine compounds

图式5. 流动电化学促进的芳烃膦酰化反应

Scheme 5. Phosphorylation of arenes under electrochemical continuous flow conditions

图式6. 锰催化的杂芳烃与二苯基磷氧化物的电化学交叉偶联反应

Scheme 6. Mn-catalyzed electrochemical cross-coupling of heteroarenes with diphenylphosphine oxides

图式7. 电催化茂金属类化合物的碳-氢膦酰化反应

Scheme 7. Electrocatalytic C—H phosphorylation of metallocenes

图式8. 电化学Rh(III)催化芳烃与二苯基氧化膦的脱氢偶联反应

Scheme 8. Rh(III)-catalyzed electrochemical dehydrogenative coupling of arenes with diphenylphosphine oxides

图式9. 电化学镍催化的(杂)芳烃膦酰化反应

Scheme 9. Ni-catalyzed electrochemical phosphorylation of (hetero)arenes

图式10. 电化学Ru催化芳烃化合物邻/对位选择性C—H膦酰化反应

Scheme 10. Ru-catalyzed electrochemical ortho/para-selective C—H phosphorylation of arenes

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