基于电化学合成的Minisci反应研究进展

doi:10.6023/cjoc202603033

摘要/Abstract

电化学条件下的Minisci反应, 作为杂环化合物C—H官能团化的绿色高效策略, 凭借无需额外氧化剂、条件温和、原子经济性高等优势, 近年来在有机合成与药物研发领域备受关注. 该反应核心是通过电极过程调控自由基生成, 实现亲核碳自由基与质子化缺电子杂环的选择性加成, 有效解决了传统Minisci反应底物范围窄、副产物多等问题. 近年研究亮点还包括多组分体系、光电协同催化体系构建等策略的探索, 显著拓展了反应适用性与应用场景. 现有综述多覆盖2022年前研究或光诱导体系, 对近期电化学驱动反应的新策略、新进展总结不足. 本工作系统综述2022年以来电化学条件下Minisci反应的最新研究成果, 为相关领域的分子合成与结构修饰提供参考.

关键词: Minisci反应, 电化学合成, 氢原子转移, 自由基加成

As a green and efficient strategy for the C—H functionalization of heterocyclic compounds, the electrochemical Minisci reaction has attracted considerable attention in the fields of organic synthesis and pharmaceutical research in recent years, owing to its advantages such as no need for additional oxidants, mild reaction conditions, and high atom economy. The core of this reaction lies in regulating radical generation via electrode processes to achieve the selective addition of nucleo-philic carbon radicals to protonated electron-deficient heterocycles, which effectively addresses the limitations of the traditional Minisci reaction, including a narrow substrate scope and numerous by-products. Recent research highlights also involve the exploration of strategies such as the construction of multicomponent systems and photoelectric synergistic catalytic systems, which have significantly expanded the reaction applicability and application scenarios. Most existing reviews cover research prior to 2022 or photoinduced systems, and lack a comprehensive summary of the new strategies and advances in electrochemically driven reactions in recent years. This work systematically reviews the latest research advances in the Minisci reaction under electrochemical conditions since 2022, providing a reference for molecular synthesis and structural modification in related fields.

Key words: Minisci reaction, electrochemical synthesis, hydrogen atom transfer (HAT), radical addition

引用此文

伍智林, 邓美琪, 丁柔, 王祖利. 基于电化学合成的Minisci反应研究进展[J]. 有机化学, 2026, 46(10): 3889-3903.

Zhilin Wu, Meiqi Deng, Rou Ding, Zuli Wang. Advances in Minisci Reactions Based on Electrochemical Synthesis[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 3889-3903.

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图/表 16

图式1. Minisci型反应的常见机理路径概述

Scheme 1. General overview of common mechanistic pathways in Minisci-type reactions

图式2. 基于碘代烷烃产生烷基自由基

Scheme 2. Generation of alkyl radicals from iodoalkanes

图式3. 三甲基硅基叠氮为HAT催化剂的烷基化反应

Scheme 3. Alkylation using TMSN3 as a HAT catalyst

图式4. 活性玻碳电极作为HAT催化剂的烷基化反应

Scheme 4. Alkylation using glassy carbon electrode as a HAT catalyst

图式5. 其他烷基化反应

Scheme 5. Other alkylation reactions

图式6. 三组分Minisci型反应

Scheme 6. Three-component Minisci-type reaction

图式7. 配对电解驱动的三组分Minisci型反应

Scheme 7. Paired electrolysis enabled three-component Minisci-type reaction

图式8. 喹喔啉(酮)类化合物与芳基肼盐酸盐的电化学氧化C—H芳基化反应

Scheme 8. Electrochemical oxidative C—H arylation of quinoxalin(on)es with arylhydrazine hydrochlorides

图式9. 基于氰基芳烃还原产生芳基自由基

Scheme 9. Generation of aryl radicals from the reduction of cyanoarenes

图式10. 基于α-酮酸脱羧产生酰基自由基

Scheme 10. Generation of acyl radicals based on the decarboxylation of α-keto acids

图式11. 基于醛基HAT产生酰基自由基

Scheme 11. Generation of acyl radicals via HAT of the aldehyde group

图式12. 酰肼为酰基源的Minisci酰基化反应

Scheme 12. Minisci acylation with acylhydrazines as acyl source

图式13. 基于C—C键裂解产生酰基自由基

Scheme 13. Generation of acyl radicals via C—C bond cleavage

图式14. 以NHPI为HAT催化剂的电化学硅烷基化反应

Scheme 14. Electrochemical silylation reaction with NHPI as the HAT catalyst

图式15. 氮杂尿嘧啶与氢硅烷的电化学C—H键硅基化反应

Scheme 15. Electrochemical C—H silylation of azauracils with hydrosilanes

图式16. 氯促进的光电化学C—H键硅烷基化反应

Scheme 16. Chloride-promoted photoelectrochemical C—H silylation

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