碳氮键参与的电化学阴极还原反应研究进展

doi:10.6023/cjoc202310036

摘要/Abstract

含有碳氮键的化合物如胺、亚胺、腈与氮杂芳环等广泛存在于自然界中, 并在药物、农药和材料等领域中发挥关键作用, 研究碳氮键参与的反应具有重要意义. 在有机合成反应中, 利用碳氮键的还原反应可以脱除保护基、实现官能团转化和构建生物活性分子等. 然而碳氮键特别是碳氮单键通常具有一定的化学稳定性, 导致碳氮键还原反应往往需要在苛刻的条件下进行. 近年来, 随着有机电化学合成研究的兴起, 采用温和的电化学反应途径选择性地还原碳氮键受到了研究者的更多关注. 根据底物结构的不同, 碳氮键参与的电化学阴极还原反应可以分为饱和碳氮键和不饱和碳氮键参与的阴极还原反应两大类. 含饱和碳氮键的化合物如铵盐、酰胺、氮丙啶和硝基化合物等, 其阴极还原反应涉及碳氮键的断裂和官能团的取代. 含不饱和碳氮键的化合物如亚胺、肟和氮杂环等, 通常会被还原为碳氮单键中间体随后发生加成. 简要综述了上述两大类底物的阴极还原反应, 并总结了可能的反应机理.

关键词: 有机电化学, 阴极还原, 碳氮键, 自由基离子

Compounds containing carbon-nitrogen bonds, such as amines, imines, nitriles, and N-heterocycles, are widespread in nature and play essential roles in pharmaceuticals, pesticides, materials, and other fields. The investigation of reactions involving carbon-nitrogen bonds is of paramount significance. In organic synthesis, the reduction of carbon-nitrogen bonds can be used for the removal of protecting groups, conversion of functional groups, and construction of biologically active molecules. However, carbon-nitrogen bonds, especially carbon-nitrogen single bonds, are renowned for their notable stability, thus requiring the harsh conditions for their reductions. As the renaissance of organic electrosynthesis in recent years, the electrochemical cathodic reductive reactions of carbon-nitrogen bonds under mild conditions have garnered considerable attention. According to the molecular structure of the substrates, electrochemical cathodic reductive reaction involving carbon-nitrogen bonds can be classified into two major categories: reductions of saturated carbon-nitrogen bonds, and unsaturated carbon-nitro- gen bonds. For compounds with saturated carbon-nitrogen bonds, such as ammonium salts, amides, aziridines, and nitro compounds, their cathodic reductions usually involve the cleavage of carbon-nitrogen bonds and substitution of the N-contained functional group. Compounds with unsaturated carbon-nitrogen bonds, such as imines, oximes, and N-heterocycles, are typically reduced into intermediates containing carbon-nitrogen single bonds, followed by addition reactions. A concise overview of the cathodic reductive reactions of above two kinds of substrates is provided and the possible reaction mechanisms is summarized.

Key words: organic electrochemistry, cathodic reduction, carbon-nitrogen bond, radical ions

引用此文

黄健, 张文珍. 碳氮键参与的电化学阴极还原反应研究进展[J]. 有机化学, 2024, 44(3): 825-839.

Jian Huang, Wenzhen Zhang. Advances in Electrochemical Cathodic Reductive Reactions Involving Carbon-Nitrogen Bonds[J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 825-839.

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图/表 30

图式1. 碳氮键参与的两类电化学阴极还原反应

Scheme 1. Eectrochemical cathodic reductive reactions involving carbon-nitrogen bonds

图式2. 苄基铵盐与CO2的电化学羧化反应

Scheme 2. Cathodic carboxylation of benzyl ammonium salts with CO2

图式3. 芳基/苄基铵盐的电化学硼化反应

Scheme 3. Electrochemical borylation of aryl/benzyl ammonium salts

图式4. 芳基/苄基铵盐的电化学氰化与氰甲基化反应

Scheme 4. Electrochemical cyanation and cyanomethylation of aryl/benzyl ammonium salts

图式5. 电化学镍催化芳基铵盐的脱羧交叉偶联

Scheme 5. Electrochemical Ni-catalyzed decarboxylative cross coupling of aryl ammonium salts

图式6. 芳基重氮盐参与的阴极还原反应

Scheme 6. Cathodic reduction involving aryl diazonium salts

图式7. 芳基偶氮砜的电化学硫化和硼化反应

Scheme 7. Electrochemical thiolation and borylation of arylazo sulfones

图式8. 甲酰胺与苯乙酮的电化学反应

Scheme 8. Electrochemical reaction of formamide and acetophenone

图式9. 阴极还原断裂N-苯基酰胺的C—N键

Scheme 9. C—N bond cleavage in N-phenylamide during cathodic reduction

图式10. Katritzky盐的电化学脱氨基偶联

Scheme 10. Electrochemical deaminative coupling using Katritzky salt

图式11. Katritzky盐脱氨基偶联机理

Scheme 11. The mechanism of electrophotochemical radical recycling in deamination coupling reaction using Katritzky salt

图式12. 镍催化芳基氮丙啶与烯丙基溴化物的电还原交叉偶联

Scheme 12. Nickel-catalyzed electroreductive cross coupling of aryl aziridines with allyl bromides

图式13. 镍催化芳基氮丙啶与芳基碘化物的电还原交叉偶联

Scheme 13. Nickel-catalyzed electroreductive cross coupling of aryl aziridines with aryl iodides

图式14. 镍催化氮丙啶与芳基溴化物的电还原交叉偶联

Scheme 14. Nickel-catalyzed electroreductive cross coupling of aziridines with aryl bromides

图式15. 芳基氮丙啶与芳基溴化物的电还原交叉偶联

Scheme 15. Electroreductive cross coupling of aryl aziridines with aryl bromides

图式16. 硝基芳烃的电化学硼化反应

Scheme 16. Electrochemical borylation of nitroarenes

图式17. 硝基甲烷参与的异噁唑啉醛肟的电化学合成

Scheme 17. Electrochemical synthesis of isoxazoline aldoximes involving nitromethane.

图式18. 阴极还原肟制备手性胺类化合物

Scheme 18. Cathodic reduction of oximes for the synthesis of chiral amine compounds

图式19. 亚胺的电还原羧化反应合成N-溴代氨基酸

Scheme 19. Electroreductive carboxylation of imines for the synthesis of N-brominated amino acids

图式20. N-酰基亚胺与CO2的电还原羧化反应

Scheme 20. Electroreductive carboxylation of N-acylimines with CO2

图式21. N-酰基亚胺与CO2的电还原羧化可能的反应机理

Scheme 21. Possible reaction mechanism for electroreductive carboxylation of N-acylimines with CO2

图式22. 电还原亚胺盐酸盐与杂环化合物合成受阻胺

Scheme 22. Electroreductive synthesis of hindered amines from imine hydrochloride and heterocycles

图式23. 亚胺与杂环的电还原交叉偶联制备苄胺

Scheme 23. Electroreductive cross-coupling of imines and heterocycles for the preparation of benzylamines

图式24. 亚胺与醛的电化学Aza-pinacol偶联

Scheme 24. Electrochemical Aza-pinacol coupling of imines with aldehydes

图式25. N-酰基二芳基亚胺与醛的电化学偶联

Scheme 25. Electrochemical coupling of N?acyl diarylketimines with aldehydes

图式26. N-酰基二芳基亚胺与醛的电化学偶联反应机理

Scheme 26. Mechanism of electrochemical coupling of N?acyl diarylketimines with aldehydes

图式27. N-芳基醛亚胺与酮的电化学aza-pinacol偶联

Scheme 27. Electrochemical aza-pinacol coupling of N-aryl aldimines with ketones

图式28. 硝酮参与的电化学阴极还原反应

Scheme 28. Electrochemical cathodic reduction involving nitrones

图式29. 氮杂芳环与醛/酮或烯烃的电还原交叉偶联反应

Scheme 29. Electrocatalytic cross-coupling of N-heteroaroma- tics with aldehydes/ketones or olefins

图式30. 氮杂芳环与醛/酮的电还原交叉偶联反应机理

Scheme 30. Mechanism of the electrocatalytic cross-coupling of N-heteroaromatics with aldehydes/ketones

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