电子上转换的基本原理及其在有机催化中的应用

doi:10.6023/cjoc202506036J

摘要/Abstract

光子上转换(Photon upconversion)作为一种突破斯托克斯限制的光子能量增益技术, 已在发光材料与器件领域展现出重要应用价值. 受此物理过程的启发, 化学家近年来将其核心概念拓展至有机催化领域, 由此衍生出电子上转换(Electron upconversion)这一创新催化范式. 该策略通过电子作为催化媒介, 实现反应物向产物的高效转化. 相较于基态转化过程, 自由基转化过程的放能更小, 速率更快; 反应过程中产生的上转换中间体通过将电子传递给原料来完成催化循环. 目前发展的电子上转换策略主要包括: 分子解离型(如单分子均裂过程, 分子缔合型(如形成双分子三电子键), 超级电子供体体系等. 这些策略已成功应用于C—N偶联, Si—Si键活化等重要有机反应中, 为绿色催化提供了新思路. 此文详细介绍了其理论机制(包括热力学和动力学基础), 反应类型以及在催化合成中的应用, 概述了相关领域的发展前沿.

关键词: 电子上转换, 解离, 缔合, 超级电子供体, 还原剂

Photon upconversion, an anti-Stokes process that elevates photon energy, has become indispensable in photonic materials and optoelectronic devices. Inspired by this physical phenomenon, chemists have recently transposed its fundamental concept to organic catalysis, establishing electron upconversion as an innovative catalytic paradigm. The thermodynamic and kinetic advantages of electron upconversion originate from two key features: (1) Radical transformations exhibit significantly reduced energy release and accelerated reaction rates compared to ground-state processes; (2) The upconverted intermediates complete catalytic cycles via facile electron transfer mechanisms. Three principal electron upconversion strategies have been developed: molecular dissociation (e.g., homolytic bond cleavage), molecular association (e.g., three-electron bond formation), and super-electron-donor systems. These groundbreaking approaches have demonstrated remarkable efficacy in pivotal organic transformations including C—N cross-coupling and Si—Si bond activation, opening new avenues for sustainable catalysis development. This article provides a comprehensive discussion of the theoretical mechanisms (including thermodynamic and kinetic fundamentals), reaction types, and applications in catalytic synthesis, while also summarizing cutting-edge developments in related fields.

Key words: electron upconversion, dissociation, association, super-electron-donors, reductants

引用此文

朱文慧, 杨金东. 电子上转换的基本原理及其在有机催化中的应用[J]. 有机化学, 2025, 45(11): 3937-3952.

Wenhui Zhu, Jin-Dong Yang. Fundamentals of Electron Upconversion and Its Applications in Organocatalysis[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 3937-3952.

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图/表 27

图式1. TTA-UC机理

Scheme 1. Mechanism diagram of TTA-UC

图式2. 电化学催化反应实例

Scheme 2. Examples of electrochemical catalysis

图式3. 光子上转换和电子上转换的类比(Ered=reductive potential)

Scheme 3. Analogy between photon and electron upconversion (Ered=reductive potential)

图式4. 还原剂上转换的热力学基础

Scheme 4. Thermodynamics of upconversion on reductants

图式5. 解离型上转换的三种类型

Scheme 5. Three types of dissociative upconversion

图式6. N-苄氧基邻苯二甲酰亚胺的电催化还原机制图

Scheme 6. Electrocatalytic reduction mechanism of N-benzyloxyphthalimide

图式7. α-氨基烷基自由基催化的杂芳基和芳基偶联

Scheme 7. Mechanism of heteroaryl and aryl coupling catalyzed by α-aminoalkyl radicals

图式8. 偶氮硫化物的还原剂上转换机制图

Scheme 8. Mechanistic diagram of reductant upconversion of azo sulfides

图式9. 环过氧化物的还原剂上转换机制图

Scheme 9. Mechanistic diagram of reductant upconversion of cycloperoxide

图式10. 碱催化的自由基烯丙基化机理图及理论计算结果

Scheme 10. Mechanistic diagram and theoretical calculations of base-catalyzed radical allylation

图式11. 蒽醌及其衍生物的电催化链式反应机理图

Scheme 11. Electrocatalytic chain reaction mechanism diagram of anthraquinone and its derivatives

图式12. 基于2c, 3e键上转换的轨道相互作用分析

Scheme 12. Orbital interaction analysis of upconversion based on 2c, 3e bond

图式13. 巯基和炔烃偶联反应的机理图

Scheme 13. Mechanistic diagram of sulfhydryl and alkyne coupling reaction

图式14. 芳基卤化物的羟基化机理图

Scheme 14. Mechanism of hydroxylation of aryl halides

图式15. 有机超级电子供体分子结构及其还原性的来源

Scheme 15. Molecular structures of organic super electron donors and the origin of their reducibility

图式16. 苯并咪唑结构的SED的催化机理与底物范围

Scheme 16. Catalytic mechanism of benzimidazole-based SED and substrate scope

图式17. 在NHC催化下醛的还原剂上转换机理图

Scheme 17. Mechanism diagram for the upconversion of aldehydes catalyzed by NHC

图式18. 基于吡啶/二硼/甲醇盐体系的SED分子结构

Scheme 18. Molecular structures of SED based on pyridine/diboron/methanol salt system

图式19. 模块化的光氧化还原SED体系(Sub=substrate)

Scheme 19. Modularized photoredox SED system (Sub=substrate)

图式20. C—N键形成的两种反应路径

Scheme 20. Two types of reaction paths for C—N bond formation

图式21. 两种C—N键环化反应途径的比较

Scheme 21. Comparison of two types of C—N bond cyclization reaction pathways

图式22. Si—Si键活化转换的电子催化和空穴催化机理

Scheme 22. Electron- and hole-catalysis mechanisms of Si—Si bond activations

图式23. 碱促进的均裂芳香取代反应机理

Scheme 23. Mechanism of base-promoted homolytic aromatic substitution reactions

图式24. 光氧化还原诱导的BHAS上转换体系

Scheme 24. Photoredox-induced BHAS upconversion system

图式25. CO2自由基阴离子上转换催化芳基卤化物的还原

Scheme 25. Reduction of aryl halides catalyzed by CO2 radical anion

图式26. 电子上转换体系电位汇总

Scheme 26. Summary of potentials for electron upconversion systems

图式27. 三种上转换体系引发的催化循环

Scheme 27. Catalytic cycles triggered by three types of upconversion systems

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