光介导氨及其等价体参与的碳氮成键反应研究进展

doi:10.6023/cjoc202405038

摘要/Abstract

有机含氮化合物广泛存在于天然产物、药物分子和材料等功能分子中. 因此, 从简单易得的原料出发, 发展绿色、高效地构建C—N键的方法具有重要意义. 光是一种广泛存在且具有丰富易得、绿色经济和可再生等特点的自然资源. 另外, 氨及其等价体作为固氮的直接产物, 是一种极为经济、易得且稳定的含氮无机化合物, 也是一类理想的潜在氮来源. 将氨及其等价体中的氮原子高效转移到各种有机化合物中, 将间接实现固氮转化, 进而实现将氮气转移到有机化合物中. 因此, 利用光催化发展氨及其等价体参与的C—N成键反应具有重要的研究价值. 系统综述了近年来光介导氨及其等价体参与的碳氮成键反应进展, 并展望了氨、无机铵盐等在光催化下参与C—N成键的应用前景.

关键词: 光催化, 碳氮成键反应, 氨, 铵盐, 自由基反应

N-Containing organic compounds are widespread in natural products, drug molecules and organic materials. Therefore, it is of great importance to develop environmentally benign and efficient methods for constructing C—N bonds from simple and easily-available starting materials. Light is a widespread natural resource that is abundant, economical, and renewable. In addition, ammonia and its equivalents, as direct products of nitrogen fixation, are extremely economical and stable nitrogen-containing inorganic compounds, which serve as ideal sources of nitrogen. The efficient transfer of nitrogen atom from ammonia and its equivalents to diverse organic compounds represents the transfer of nitrogen from inorganic compounds to organic compounds resulting from the fixation of nitrogen gas. Therefore, it is of great value to develop the C—N bonding reaction involving ammonia and its equivalents by photocatalysis. The progress of light-catalyzed carbon-nitrogen bond-forming reactions involving ammonia and its equivalents over recent years is summarized. Moreover, a prospective on the further development of ammonia and inorganic ammonium salts for C—N bond-formation by photocatalysis is discussed.

Key words: photocatalysis, C—N bond-forming reaction, ammonia, ammonium salt, radical reaction

引用此文

李顺曦, 游力栩, 李玉龙, 舒伟. 光介导氨及其等价体参与的碳氮成键反应研究进展[J]. 有机化学, 2025, 45(5): 1460-1477.

Shunxi Li, Lixu You, Yulong Li, Wei Shu. Recent Progress on Light-Mediated C—N Bond-Forming Processes from Ammonia and Equivalents[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1460-1477.

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图/表 35

图式1. 光催化氨及其等价体参与的碳氮成键反应

Scheme 1. Light-mediated C—N bond-forming reactions from ammonia its equivalents

图式2. 紫外光催化芳基环丙烷和芳基烯烃氢胺化制备伯胺

Scheme 2. UV-light-catalyzed hydroamination of arylpropanes and styrenes for primary amines

图式3. 无过渡金属参与的光催化制备腈的反应

Scheme 3. Photocatalytic metal-free synthesis of nitriles

图式4. 无金属试剂条件下实现一锅法从甲基芳烃合成芳香腈

Scheme 4. Metal-free and one-pot protocol for the synthesis of aryl nitrile from methylarenes

图式5. 紫外-可见光催化氨的N-甲基化反应

Scheme 5. N-Methylation of ammonia catalyzed by UV-visible light

图式6. 可见光催化烯烃1,2-二氟甲基氰基化反应

Scheme 6. Visible-light-catalyzed 1,2-cyanodifluoromethylation of olefins

图式7. 光催化苄醇与氨氧化缩合制备腈

Scheme 7. Photocatalyzed oxidative condensation of benzyl alcohols with ammonia to nitrile

图式8. 光催化从甲醇和氨制备HMT的反应

Scheme 8. Photocatalytic synthesis of HMT from methanol and ammonia

图式9. 可见光催化烯丙基C—H直接胺化反应

Scheme 9. Visible-light-catalyzed direct amination of allylic C—H bonds

图式10. 紫外光催化富电子苯乙烯与氨的氢胺化制备伯胺

Scheme 10. UV-light-catalyzed hydroamination of electron-rich styrenes and ammonia to access primary amines

图式11. 紫外光催化2-烯基萘与氨的区域选择性氢胺化反应

Scheme 11. UV-light-catalyzed regioselective hydroamination of 2-vinylnaphthene with ammonia

图式12. 可见光催化从醛酮和氨合成无保护伯胺

Scheme 12. Visible-light-catalyzed synthesis of unprotected primary amines from carbonyls and ammonia

图式13. 光催化烯烃反马式氢胺化反应

Scheme 13. Photocatalytic anti-Markovnikov hydroamination of olefins

图式14. 可见光催化N-酰基烯胺与氨的氢胺化反应

Scheme 14. Visible-light-catalyzed hydroamination of N-acylenamines with ammonia

图式15. 可见光催化烯烃与铵盐的氢胺化反应合成烷基伯胺

Scheme 15. Visible-light-catalyzed hydroamination of olefins with ammonium salts to aliphatic primary amines

图式16. 有机光催化[1＋2＋3]策略一步合成2-哌啶酮衍生物

Scheme 16. Organic photocatalyzed one-step synthesis of 2-piperidones by [1＋2＋3] strategy

图式17. 可见光催化1,3-丁二烯与氨的区域选择性氢胺化反应

Scheme 17. Visible-light-catalyzed regioselective hydroamination of 1,3-dienes with ammonia

图式18. Pt/TiO2紫外光催化合成芳基伯胺的反应

Scheme 18. Pt/TiO2-catalyzed synthesis of primary aryl amines under UV light

图式19. 可见光催化(杂)芳烃与铵盐的碳氢胺化反应

Scheme 19. Visible-light-catalyzed C—H amination of (hetero)arenes with ammonium salts

图式20. 可见光催化呋喃转化为内酰胺的反应

Scheme 20. Visible-light-catalyzed conversion of furans to lactams

图式21. 可见光催化苯与氨的析氢碳氮偶联反应

Scheme 21. Visible-light-catalyzed C—H amination of arenes with ammonia by releasing H2

图式22. 紫外光催化Ullmann-Goldberg偶联生成芳基伯胺

Scheme 22. UV light-catalyzed Ullmann-Goldberg coupling to aryl primary amines

图式23. 紫外光催化合成α-酮酰胺的反应

Scheme 23. UV light-catalyzed synthesis of α-ketoamide

图式24. 可见光催化富电子芳烃与铵盐的碳氢胺化反应

Scheme 24. Visible-light-catalyzed C—H amination of electron- rich arenes with ammonium salts

图式25. 可见光和钴协同催化环己酮与氨脱氢芳香化制备苯胺

Scheme 25. Visible-light and cobalt-catalyzed dehydrogenative aromatization of cyclohexanones with ammonia to anilines

图式26. 可见光催化无机铵盐与芳烃碳氟键的取代伯胺化反应

Scheme 26. Visible light catalyzed substitution of aromatic carbon-fluorine bonds with inorganic ammonium salts for the synthesis of primary anilines

图式27. 可见光催化芳酰氯与氨的C—N偶联反应

Scheme 27. Visible-light-catalyzed C—N coupling of aryl chloride with ammonia

图式28. 可见光和钴协同催化芳基羧酸与氨发生酰胺化反应

Scheme 28. Visible-light and Co-catalyzed amidation of aryl carboxylic acids and ammonia

图式29. Ti-V-MCM-41紫外光催化苯和氨直接制备苯胺

Scheme 29. Ti-V-MCM-41-catalyzed C—H amination of benzene with ammonia under UV light

图式30. 镍和可见光协同催化芳基卤化物与铵盐的C—N偶联反应

Scheme 30. Visible-light and Ni-catalyzed C—N cross-coupling of aryl halides with ammonium salt

图式31. Werner盐作为镍和氨源光催化合成芳基伯胺

Scheme 31. Photo- and Ni-catalyzed synthesis of primary aryl amines using Werner salts as both nickel and nitrogen

图式32. 可见光催化烯基三氟甲基与铵盐的全脱氟键偶联合成酰胺

Scheme 32. Visible-light-catalyzed exhaustive defluorinative coupling of vinyl trifluorides with ammonium salts for the synthesis of amides

图式33. 可见光催化铵盐与联芳烃合成菲咯啶

Scheme 33. Visible-light-catalyzed synthesis of phenanthrdines from biaryl aldehydes with ammonium salts

图式34. 光和钴协同催化烯烃、一氧化碳和氨合成酰胺

Scheme 34. Photo- and Co-catalyzed synthesis of amides from alkenes, carbon monoxide and ammonia

图式35. 可见光与碘催化末端炔与氨氧化合成酰胺

Scheme 35. Visible-light and iodine-catalyzed oxidative synthesis of amides from terminal alkynes with ammonia

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