Red Light-Mediated Organic Synthesis Reactions

doi:10.6023/cjoc202604030

Abstract

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

Cite this article

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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Fig. & Tab. 45

Scheme 1. Two common mechanism in photocatalysis

Scheme 2. Commonly used PCs and advantages of red light

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

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

Scheme 4. Dehalogenative hydrogenation reaction based on thioporphyrins

Scheme 5. Radical cascade perfluoroalkylation reaction catalyzed by zinc phthalocyanine

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

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

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

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

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

Scheme 11. H2TPP catalyzed functionalization of biomolecules

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

Scheme 13. Osmium complex catalyzed regioselective sulfonyltrifluoromethylation of alkenes

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

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

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

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

Scheme 18. ZnTPP catalyzed radical Giese addition

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

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

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

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

Scheme 23. Ruthenium phthalocyanine catalyzed chlorotrifluoromethylation of alkenes

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

Scheme 25. Osmium complex catalyzed oxidative decarboxylation of oxamic acid

Scheme 26. Chlorophyll catalyzed aerobic oxidative hydroxylation of organoboron compounds

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

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

Scheme 29. Ruthenium phthalocyanine catalyzed difunctionalization of alkenes

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

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

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

Scheme 33. Zinc phthalocyanine catalyzed oxidative cyanation of tertiary amines

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

Scheme 35. ZnTPP catalyzed decarboxylative functionalization of barton esters

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

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

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

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

Scheme 40. Chlorophyll catalyzed Barton-McCombie deoxygenation reaction

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

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

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

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

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红光介导有机合成反应