红光介导有机合成反应

doi:10.6023/cjoc202604030

摘要/Abstract

光化学领域的迅猛发展为可见光介导的有机合成带来了诸多技术突破, 其中红光因具有波长较长、光子能量较低、对生物体系损伤小且反应副产物少的独特优势, 已成为该领域的研究热点之一. 与传统紫外光及蓝光催化体系相比, 红光催化能够以更温和的方式实现有机反应的高效、可控进行, 有效避免非特异性副反应的发生. 基于此, 系统梳理了近年来红光介导有机合成反应的研究进展, 依据反应的核心作用机理, 将其划分为单电子转移、能量转移、金属键均裂、底物直接激发及光酶催化五大类型, 并对各类反应的具体反应路径、调控规律及作用机理展开系统阐述与深入探讨, 以期为红光介导有机合成的后续研究与应用提供理论参考和研究思路.

关键词: 红光, 有机合成, 自由基, 反应机理

The rapid advancement of photochemistry has enabled significant technological breakthroughs in visible light-mediated organic synthesis. Among these advances, red light has emerged as a focal area of research due to its distinctive photophysical and biological advantages: longer wavelength, lower photon energy, minimal phototoxicity toward biological systems, and reduced generation of undesired side products. Compared with conventional ultraviolet (UV) and blue light-driven catalytic systems, red light-mediated catalysis permits efficient and selective organic transformations under mild reaction conditions, thereby suppressing non-specific side reactions and enhancing synthetic control. In this review, recent developments in red light-driven organic synthesis are systematically surveyed. Reactions are classified into five mechanistic categories: single-electron transfer (SET), energy transfer (EnT), metal-ligand bond homolysis, direct substrate excitation, and photoenzymatic catalysis. For each category, we provide a rigorous analysis of representative transformations, key operational parameters governing selectivity and efficiency, and current mechanistic understanding. Collectively, this work offers a consolidated conceptual framework and identifies promising avenues for future investigation and practical implementation of red light-enabled synthetic methodologies.

Key words: red light, organic synthesis, radical, reaction mechanism

引用此文

张令红, 孔慢慢, 张曌霞, 江智勇. 红光介导有机合成反应[J]. 有机化学, 2026, 46(10): 3804-3837.

Linghong Zhang, Manman Kong, Zhaoxia Zhang, Zhiyong Jiang. Red Light-Mediated Organic Synthesis Reactions[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 3804-3837.

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图/表 45

图式1. 光催化中两种常见的机理

Scheme 1. Two common mechanism in photocatalysis

图式2. 常用的PC与红光的优点

Scheme 2. Commonly used PCs and advantages of red light

图式3. 常用的红光光敏剂

Scheme 3. Common red light photosensitizers

对比维度	红光催化(600~700 nm)	蓝光催化(400~500 nm)
光波长及能量	600~700 nm, 1.7~2.1 eV(低能量)	400~500 nm, 2.6~3.1 eV(中高能量)
反应路径	以电子转移为主, 能量转移较少	电子转移与能量转移均常见
常用催化剂	Os(II)配合物、有机光敏染料	Ru(II)配合物、Ir(III)配合物、有机荧光染料
能级匹配要求	能量转移需严格匹配, 电子转移对能级匹配要求宽松	能量转移对能级匹配要求高, 电子转移适配范围广
适用反应类型	交叉偶联、氧化还原环化、自由基加成(电子转移型)	烯烃异构化、敏化发光、单线态氧生成(能量转移型); 交叉偶联、氧化(电子转移型)
副反应情况	低能量导致副反应少(如过度氧化、键断裂)	能量较高, 部分反应易出现过度反应、底物分解
反应条件	温和, 无需苛刻氛围(部分可在空气下进行)	大部分反应需惰性氛围, 避免氧气干扰能量转移

表1. 红光催化与蓝光催化的不同

Table 1. Comparison of red-light and blue-light photocatalysis

图式4. 基于硫代卟啉的脱卤氢化反应

Scheme 4. Dehalogenative hydrogenation reaction based on thioporphyrins

图式5. 锌酞菁催化下自由基串联全氟烷基化反应

Scheme 5. Radical cascade perfluoroalkylation reaction catalyzed by zinc phthalocyanine

图式6. 亚甲基蓝催化氮杂环的选择性开环与内酰胺合成

Scheme 6. Methylene blue catalyzed selective ring-opening of N-heterocycles and lactam synthesis

图式7. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$催化芳基C—H官能团化及脱硼羟基化反应

Scheme 7. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$ catalyzed aryl C—H functionalization and deborylative hydroxylation

图式8. 基于锡-二氢卟酚催化剂的红光驱动邻近标记平台的反应机理

Scheme 8. Proximity labeling platform based on a Sn-chlorin photocatalyst

图式9. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$催化[3＋2]环加成反应

Scheme 9. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$ catalyzed [3＋2] cycloaddition reaction

图式10. Os配合物催化C—N键的交叉偶联反应

Scheme 10. Os complex catalyzed cross-coupling of C—N bonds

图式11. 四苯基卟啉类化合物催化生物分子功能化

Scheme 11. H2TPP catalyzed functionalization of biomolecules

图式12. 亚甲基蓝(MB)催化苯基自由基机制介导的硼酸前药的光活化反应

Scheme 12. MB catalyzed photoactivation of boronic acid prodrugs via phenyl radical mechanism

图式13. Os配合物催化烯烃的区域选择性磺酰三氟甲基化反应

Scheme 13. Osmium complex catalyzed regioselective sulfonyltrifluoromethylation of alkenes

图式14. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$催化红光介导的卤素原子转移芳基碘化物选择性活化

Scheme 14. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$ catalyzed red light-mediated halogen atom transfer for selective activation of aryl iodides

图式15. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$催化吲哚C-3位甲酰化反应

Scheme 15. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$ catalyzed C3 formylation of indole

图式16. mpg-CN催化对映选择性Minisci加成反应

Scheme 16. mpg-CN-Ccatalyzed enantioselective Minisci-type addition

图式17. mpg-C3N4催化Minisci反应合成杂环取代双环[1.1.1]戊烷

Scheme 17. mpg-C3N4 catalyzed Minisci reaction for the synthesis of heterocycle substituted bicyclo[1.1.1]pentanes

图式18. ZnTPP催化自由基Giese加成反应

Scheme 18. ZnTPP catalyzed radical Giese addition

图式19. 四苯基卟啉催化缺电子杂环C(sp²)—H烷基化反应

Scheme 19. H2TPP catalyzed C(sp²)—H alkylation of electron-deficient heterocycles

图式20. 硅罗丹明催化的邻硝基苄基光脱笼反应

Scheme 20. Silicon rhodamine catalyzed photodecaging of ortho-nitrobenzyl groups

图式21. 亚甲基蓝催化芳基噻蒽鎓盐C—H键解笼反应

Scheme 21. MB catalyzed C—H uncaging of aryl thianthrenium salts

图式22. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$催化吲哚三氟甲基化/环化串联反应

Scheme 22. nPr-DMQA⁺${\text{BF}}_{\text{4}}^{-}$ catalyzed cascade trifluoromethylation-cyclization of indoles

图式23. 酞菁钌配合物催化烯烃的氯三氟甲基化反应

Scheme 23. Ruthenium phthalocyanine catalyzed chlorotrifluoromethylation of alkenes

图式24. Os配合物催化芳基叠氮化合物产生三重态氮宾

Scheme 24. Osmium catalyzed transformation of aryl azides to triplet nitrenes

图式25. Os配合物催化草氨酸氧化脱羧反应

Scheme 25. Osmium complex catalyzed oxidative decarboxylation of oxamic acid

图式26. 叶绿素催化有机硼化合物需氧氧化羟基化的反应

Scheme 26. Chlorophyll catalyzed aerobic oxidative hydroxylation of organoboron compounds

图式27. 锇(II)多吡啶配合物与钌协同催化的烯烃复分解反应

Scheme 27. Osmium(II) polypyridyl complex and ruthenium co-catalyzed olefin metathesis

图式28. Zn配合物催化氧化还原酯与烯烃的自由基级联反应

Scheme 28. Zn catalyzed radical cascade between redox-active esters and alkenes

图式29. 酞菁钌络合物催化烯烃双官能团化反应

Scheme 29. Ruthenium phthalocyanine catalyzed difunctionalization of alkenes

图式30. 氮杂二吡咯甲烷(ADP1)催化下有机硼化合物的配位-光解产生碳自由基

Scheme 30. ADP1 catalyzed generation of carbon radicals via coordination-photolysis of organoboron compounds

图式31. ADP1与镍协同催化烷基硼与芳基卤化物C(sp²)—C(sp³)交叉偶联反应

Scheme 31. ADP1 and nickel co-catalyzed C(sp²)—C(sp³) cross-coupling of alkylboron reagents with aryl halides

图式32. 4MeODPATPN与镍协同催化芳基卤化物的C—杂原子偶联反应

Scheme 32. 4MeODPATPN and nickel Co-catalyzed C—heteroatom coupling of aryl halides

图式33. 锌酞菁催化叔胺的氧化氰化反应

Scheme 33. Zinc phthalocyanine catalyzed oxidative cyanation of tertiary amines

图式34. RPE-(Ru)n生物杂化光催化剂催化硫醇-烯偶联与半胱氨酸脱硫反应

Scheme 34. RPE-(Ru)n biohybrid photocatalyst catalyzed thiol-ene coupling and cysteine desulfurization

图式35. 锌酞菁催化Barton酯脱羧官能化反应

Scheme 35. ZnTPP catalyzed decarboxylative functionalization of barton esters

图式36. Os(II)配合物催化重氮化合物生成卡宾

Scheme 36. Os(II) complex catalyzed carbene generation from diazo compounds

图式37. Rhodin G7催化单线态氧介导的磷(V)前药C(sp²)—P键断裂解笼反应

Scheme 37. Rhodin G7 catalyzed singlet oxygen-mediated C(sp²)—P bond cleavage uncaging of phosphorus(V) prodrugs

图式38. 铁(I)二聚体催化合成二氟甲基取代稠环喹唑啉酮类化合物

Scheme 38. Iron(I) dimer catalyzed synthesis of difluoromethyl substituted ring fused quinazolinones

图式39. 铁(I)二聚体催化环酮肟酯官能化反应

Scheme 39. Iron(I) dimer catalyzed functionalization of cyclic ketoxime esters

图式40. 叶绿素催化Barton-McCombie脱氧反应

Scheme 40. Chlorophyll catalyzed Barton-McCombie deoxygenation reaction

图式41. 铋(I)配合物催化芳基亲电试剂的氧化加成反应

Scheme 41. Bismuth (I) complex-catalyzed oxidative addition of aryl electrophiles

图式42. 基于漆酶/TEMPO协同催化氧化反应

Scheme 42. Oxidation through a Laccase/TEMPO synergistic catalysis system

图式43. 工程化光酶GluER-RED催化的自由基环化反应

Scheme 43. Radical cyclization catalyzed by the engineered photoredox enzyme GluER-RED

图式44. NMB＋双光子催化偶氮键断裂反应

Scheme 44. NMB＋ catalyzed azo bond cleavage via two-photon excitation

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