可见光促进偶氮化合物参与的光化学转化

doi:10.6023/cjoc202405022

摘要/Abstract

偶氮化合物由于其独特的结构和性质而成为有机合成中不可或缺的一部分. 他们不仅可以用作氧化剂, 还可作为偶联伙伴参与杂环合成. 近年来, 由于可见光促进的反应操作简便且条件温和, 故而受到越来越多化学工作者的关注. 如今, 可见光促进偶氮化合物参与化学转化已成为有机合成领域的热点之一, 相关的研究报道层出不穷, 例如通过偶氮化合物实现酰肼类化合物以及杂环的合成. 综述了近年来可见光促进偶氮化合物参与的光化学转化, 并对该领域所面临的挑战和机遇进行了探讨和展望.

关键词: 偶氮化合物, 可见光, 杂环合成

Azo compounds are an essential part of organic synthesis due to their unique structures and properties. They serve not only as oxidants but also as coupling partners in heterocycle synthesis. In recent years, visible-light promoted reactions have garnered increasing attention from chemists because of their convenient operation and mild reaction conditions. Nowadays, visible-light promoted chemical transformations involving azo compounds have become one of the hotspots in the field of organic synthesis, and the related research reports are emerging in endlessly. For instance, azo compounds can be used to synthesize hydrazides and heterocycles. A comprehensive review of recent advancements in visible-light promoted photochemical transformations involving azo compound is provided, while the associated challenges and potential opportunities in this field are also discussed.

Key words: azo compound, visible-light, heterocycle synthesis

引用此文

马树超, 陈泽乐, 宣俊. 可见光促进偶氮化合物参与的光化学转化[J]. 有机化学, 2025, 45(5): 1669-1683.

Shuchao Ma, Zele Chen, Jun Xuan. Visible-Light Promoted Photochemical Transformations of Azo Compounds[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1669-1683.

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图/表 30

图式1. CdS促进的偶氮苯选择性还原加氢

Scheme 1. CdS-promoted selective reductive hydrogenation of azobenzene

图式2. 曙红Y催化的偶氮苯还原加氢

Scheme 2. Eosin Y-catalyzed reductive hydrogenation of azobenzene

图式3. 可见光与联硼酸频哪醇酯结合还原偶氮苯

Scheme 3. Reduction of azobenzenes by visible light combined with B2Pin2

图式4. 偶氮苯的无金属和无催化剂还原加氢

Scheme 4. Metal- and catalyst-free reductive hydrogenation of azobenzenes

图式5. 苯甲酰甲酸催化偶氮二羧酸酯的氢酰化

Scheme 5. Hydroacylation of dialkyl azodicarboxylates catalyzed by benzoylformic acid

图式6. 石墨片介导偶氮二甲酸二异丙酯的氢酰化

Scheme 6. Graphite flakes-mediated hydroacylation of DIAD

图式7. 十钨酸盐催化偶氮二甲酸二叔丁酯的氢酰化

Scheme 7. TBADT-catalyzed hydroacylation of DBAD

图式8. 偶氮二羧酸酯与酰基硅烷的氢酰化

Scheme 8. Hydroacylation of dialkyl azodicarboxylates with acylsilanes

图式9. Ucpt催化偶氮二羧酸酯的氢酰化

Scheme 9. Ucpt-catalyzed hydroacylation of dialkyl azodicarboxylates

图式10. 偶氮苯与α-酮酸的脱羧氢酰化

Scheme 10. Decarboxylative hydroacylation of azobenzenes with α-keto acids

图式11. 三苯基膦介导偶氮苯的氢酰化

Scheme 11. PPh3-mediated hydroacylation of azobenzenes

图式12. 偶氮化合物与4-酰基取代汉斯酯的氢酰化

Scheme 12. Hydrogenation of azo compounds with 4-acyl-sub- stituted Hantzsch esters

图式13. 三氯化铈催化偶氮二羧酸酯的氢烷基化

Scheme 13. Hydroalkylation of dialkyl azodicarboxylates catalyzed by CeCl3

图式14. 通过配体到金属的电荷转移实现偶氮二甲酸二叔丁酯的氢烷基化

Scheme 14. Hydroalkylation of DBAD by LMCT

图式15. 苯并环胺作为α-氨烷基自由基前体实现偶氮二甲酸二叔丁酯的氢烷基化

Scheme 15. Hydroalkylation of DBAD using benzocyclic amines as α-aminoalkyl radical precursors

图式16. N-取代吲哚-2-羧酸作为α-氨烷基自由基前体实现偶氮二羧酸酯的氢烷基化

Scheme 16. Hydroalkylation of dialkyl azodicarboxylates using N-substituted indole-2-carboxylic acid as α-aminoalkyl radical precursors

图式17. 四氢吡咯衍生物作为α-氨烷基自由基前体实现偶氮二羧酸酯的氢烷基化

Scheme 17. Hydroalkylation of dialkyl azodicarboxylates using tetrahydropyrrole derivatives as α-aminoalkyl radical precursors

图式18. 通过构建EDA复合物产生α-氨烷基自由基

Scheme 18. Generation of α-aminoalkyl radicals by construction of EDA complexes

图式19. 甘氨酸衍生物作为α-氨烷基自由基前体实现偶氮二羧酸酯的氢烷基化

Scheme 19. Hydroalkylation of dialkyl azodicarboxylates using glycine derivatives as α-aminoalkyl radical precursors

图式20. 偶氮二羧酸酯与喹喔啉酮和苯并噁嗪酮衍生物的氢烷基化

Scheme 20. Hydroalkylation of dialkyl azodicarboxylates with quinoxalinone and benzoxazinone derivatives

图式21. rac-GW420867X的简洁合成

Scheme 21. Simple synthesis of rac-GW420867X

图式22. 偶氮苯与甘氨酸衍生物的脱羧加成环化

Scheme 22. Decarboxylative addition cyclization of azobenzenes with glycine derivatives

图式23. 偶氮苯与亚甲胺叶立德的1,3-偶极环加成

Scheme 23. 1,3-Dipolar cycloaddition of azobenzenes with azomethine ylides

图式24. 偶氮苯与苯炔的[3＋2]环加成

Scheme 24. [3＋2] cycloaddition of azobenzenes with benzynes

图式25. 无金属、无催化剂下实现2H-吲唑衍生物的合成

Scheme 25. Synthesis of 2H-indazole derivatives achieved in metal-free and catalyst-free conditions

图式26. 偶氮二羧酸酯、重氮烷烃与腈类化合物的三组分反应

Scheme 26. Three-component reactions of dialkyl azodicarboxylates, diazoalkanes and nitriles

图式27. 偶氮苯与α-酮酸的C—H酰化反应

Scheme 27. C—H acylation of azobenzenes with α-keto acids

图式28. 偶氮苯与四芳基二硼烷的二硼化反应

Scheme 28. Diboronation of azobenzenes with tetraaryl diborane

图式29. 偶氮苯与二芳基膦氧化物的氢磷化

Scheme 29. Hydrophosphorylation of azobenzenes with diarylphosphine oxides

图式30. 偶氮二羧酸酯的双官能化

Scheme 30. Difunctionalization of dialkyl azodicarboxylates

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