N-烷氧基吡啶盐参与可见光诱导反应的研究进展

doi:10.6023/cjoc202605015

摘要/Abstract

N-烷氧基吡啶盐具有结构稳定、易于制备和反应活性可调等特点, 可发生N—O键均裂, 生成烷氧基自由基和吡啶衍生物. 由于兼具烷氧自由基前体和杂芳基片段来源的双重属性, 该类化合物在自由基有机合成领域展现出独特的应用价值. 近年来, 随着可见光催化和光氧化还原体系的快速发展, N-烷氧基吡啶盐参与的自由基转化反应不断拓展, 为相关领域的合成研究提供了新策略. 此文以烷氧基自由基的主要反应模式为线索, 系统综述N-烷氧基吡啶盐在可见光诱导反应中的研究进展, 重点讨论其底物适用范围、反应机理、合成应用及方法学优势, 并对该领域未来的发展方向进行展望.

关键词: N-烷氧基吡啶盐, 可见光, 烷氧基自由基, 光氧化还原, 自由基转化

N-Alkoxypyridinium salts are characterized by structural stability and ease of preparation, and tunable reactivity. Under appropriate conditions, they undergo homolytic cleavage of the N—O bond to generate alkoxy radicals and pyridine derivatives. Owing to their dual role as alkoxy radical precursors and sources of heteroaryl fragments, these compounds have demonstrated distinctive synthetic value in radical-mediated organic transformations. In recent years, with the rapid development of visible-light catalysis and photoredox catalytic systems, radical transformations involving N-alkoxypyridinium salts have been continuously expanded, providing new strategies for synthetic research in related fields. This review summarizes recent advances in visible-light-induced reactions of N-alkoxypyridinium salts, with an emphasis on the major reaction modes of alkoxy radicals. Particular attention is paid to substrate scope, reaction mechanisms, synthetic applications, and methodological advantages. Future perspectives in this field are also discussed.

Key words: N-alkoxypyridinium salts, visible light, alkoxy radicals, photoredox, radical transformations

引用此文

王朝阳, 皮超, 密霞. N-烷氧基吡啶盐参与可见光诱导反应的研究进展[J]. 有机化学, 2026, 46(8): 2859-2891.

Chaoyang Wang, Chao Pi, Xia Mi. Recent Advances in Visible-Light-Induced Reactions Involving N-Alkoxypyridinium Salts[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 2859-2891.

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图/表 30

图式1. 可见光诱导N-烷氧基吡啶盐的转化路径

Scheme 1. Transformation pathways of N-alkoxypyridinium salts under visible light

图式2. 光氧化还原催化苯并磷杂环戊二烯氧化物的合成

Scheme 2. Visible-light photoredox-catalyzed synthesis of benzophosphole oxides

图式3. 可见光诱导EDA复合物促进N-芳基叔胺的α-C—H膦酰化

Scheme 3. Visible-light-induced EDA complex-promoted α-C—H phosphonylation of N-aryl tertiary amines

图式4. 可见光诱导吡啶类化合物的C—H硅基化/羟甲基化反应

Scheme 4. Visible-light-induced C-H silylation/hydroxymethylation of pyridine derivatives

图式5. 可见光诱导喹啉酮与香豆素的C—H键直接膦酰化

Scheme 5. Visible-light-induced direct C—H phosphonylation of quinolinones and coumarins

图式6. 可见光诱导喹啉酮介导的吡啶位点选择性C—H官能化

Scheme 6. Visible-light-induced quinolinone-mediated site-selective C-H functionalization of pyridines

图式7. 可见光激发含喹啉酮底物实现发散性自由基环化

Scheme 7. Visible-light-excited quinolinone-containing substrate enabled divergent radical cyclization

图式8. 无金属光催化非活化烯烃的三氟甲基化/吡啶化反应

Scheme 8. Metal-free photocatalytic trifluoromethylation/pyridination of unactivated alkenes

图式9. 可见光诱导吡啶的位点选择性C—H酰基化

Scheme 9. Visible-light-induced site-selective C—H acylation of pyridines

图式10. 可见光诱导C—H/X—H键的吡啶化反应

Scheme 10. Visible-light-induced pyridylation of C—H and X—H bonds

图式11. 光氧化还原催化苄位C—H键叠氮化反应

Scheme 11. Photoredox-catalyzed azolation of benzylic C—H bonds

图式12. 可见光诱导亚甲基双杂环的构建

Scheme 12. Visible-light-induced construction of methylene-bridged bisheterocycles

图式13. 光催化N-烷氧基吡啶盐介导的远端C—H键吡啶化反应

Scheme 13. Photocatalytic N-alkoxypyridinium salt-mediated remote C—H bond pyridination

图式14. 可见光/铜协同催化N-烷氧基吡啶盐介导的远端C—H键官能化反应

Scheme 14. Visible-light/copper cooperative catalysis for remote C—H functionalization mediated by N-alkoxypyridinium salts

图式15. 可见光诱导N-烷氧基吡啶盐远端C—H官能化构建δ-取代醇

Scheme 15. Visible-light-induced remote C—H functionalization of N-alkoxypyridinium salts for δ-substituted alcohols

图式16. 可见光/铜协同催化远端C—H硫代磷酸化构建δ-硫代磷酸酯醇

Scheme 16. Visible-light/copper cooperative catalysis for remote C—H thiophosphorylation for δ-thiophosphate alcohols

图式17. 光激发钯引发N-烷氧基吡啶盐的远端去饱和反应

Scheme 17. Photoexcited palladium-initiated remote desaturation of N-alkoxypyridinium salts

图式18. 光氧化还原催化氧杂环庚烷的合成

Scheme 18. Photoredox-catalyzed synthesis of oxepanes

图式19. 光氧化还原催化远端C(sp3)—H键亚磺酰化反应

Scheme 19. Photoredox-catalyzed remote C(sp3)—H sulfinylation

图式20. 光催化烷氧自由基介导的反马氏烷氧基化反应

Scheme 20. Photocatalytic alkoxy radical-mediated anti-Markovnikov alkoxylation

图式21. 可见光催化串联环化/吡啶化构建四氢呋喃骨架

Scheme 21. Visible-light-catalyzed tandem cyclization/pyridination for the construction of tetrahydrofuran scaffolds

图式22. 可见光诱导吡啶环邻位迁移实现烯烃三氟甲基化吡啶基化反应

Scheme 22. Visible-light-induced ortho-migration of pyridine ring for trifluoromethylation and pyridylation of alkenes

图式23. 可见光诱导N-烷氧基吡啶盐实现烯烃的碳吡啶化

Scheme 23. Visible-light-induced carbon-pyridylation of alkenes via N-alkoxypyridinium salts

图式24. 可见光催化三组分串联环化构建二氢苯并呋喃骨架

Scheme 24. Visible-light-catalyzed three-component tandem cyclization for the construction of dihydrobenzofuran scaffolds

图式25. 光氧化还原催化烯醛的官能化反应

Scheme 25. Photoredox-catalyzed functionalization of unbiased enals

图式26. 光催化N-烷氧基吡啶盐实现烯烃的烷氧基吡啶化

Scheme 26. Photocatalytic alkoxypyridination of alkenes using N-alkoxypyridinium salts

图式27. 可见光诱导烷氧自由基介导烯烃三官能化构建N,O-螺环缩醛胺

Scheme 27. Visible-light-induced alkoxy radical-mediated trifunctionalization of alkenes for the construction of N,O-spiroaminals

图式28. 可见光催化N-烷氧基吡啶盐与亚磷酸酯合成磷酸酯

Scheme 28. Photocatalytic synthesis of phosphates from N-alkoxypyridinium salts and phosphites

图式29. 可见光/NHC协同催化N-烷氧基吡啶盐的串联环化

Scheme 29. Visible-light/NHC cooperative catalysis enabling tandem cyclization of N-vinyloxy pyridinium salts

图式30. 可见光催化N-烷氧基吡啶盐β-断裂用于吡啶的烷基化

Scheme 30. Photocatalytic β-scission of N-alkoxypyridinium salts for alkylation of pyridines

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