电子供体-受体(EDA)复合物驱动的N-α位C—H键活化

doi:10.6023/cjoc202406050

摘要/Abstract

由电子供体-电子受体(EDA)形成的EDA复合物正在引发一个又一个神奇的光化学反应. 在可见光照射下, EDA复合物会发生单电子转移(SET)过程, 电子从供体转移向电子受体产生自由基阴阳离子对并引发后续反应. 除了光作为外部能量来源, 这一策略无需额外的光催化剂, 反应条件温和, 使得这一体系能够兼容大多数底物. 胺类化合物特别是氮杂芳烃和脂肪胺作为富电子底物, 在近年来已被广泛用于EDA复合物中的电子供体. 并且, 这类EDA复合物引发的反应中间体具有可预测性和位点选择性, 在形成EDA复合物后N-α位具有独特的反应性质, 并被用于合成复杂的含氮有机分子. 综述了含氮化合物及烷基胺作为EDA电子供体来构建N-α位C—X键(X=C, N)的光化学反应, 并对该领域的发展进行了展望.

关键词: 电子供体-电子受体(EDA)复合物, 光化学, 自由基, 胺类化合物, C—H键活化

Electron donor-acceptor (EDA) complexes formed by electron donors and electron acceptors are triggering many amazing photochemical reactions. Under visible light irradiation, the EDA complexes undergo a single electron transfer (SET) process, in which electrons are transferred from the donor to the electron acceptor to create free radical anion-cation pairs and initiate subsequent reactions. This strategy does not require an additional photocatalyst under mild reaction conditions with light as an external energy source, making this system compatible well with most substrates. Amines, such as aza-aromatics and aliphatic amines, have been widely used as electron-rich substrates as electron donors in EDA complexes in recent years. Moreover, the reaction intermediates initiated by these EDA complexes are predictable and site-selective, with unique reactive properties at the N-α position after the formation of EDA complexes, and have been used in the synthesis of complex nitrogen-containing organic molecules. The photochemical reactions of nitrogen-containing aromatics and amines as EDA electron donors for the construction of C—X bonds (X=C, N) at the N-α position are reviewed, and an outlook for the development of this field is provided.

Key words: electron donor-acceptor (EDA) complexes, photochemistry, radical, amine compounds, C—H bond activation

引用此文

杨俊峰, 赵艳秋, 时磊. 电子供体-受体(EDA)复合物驱动的N-α位C—H键活化[J]. 有机化学, 2025, 45(2): 559-573.

Junfeng Yang, Yanqiu Zhao, Lei Shi. Electron Donor-Acceptor (EDA) Complex-Driven Activation of N-α C—H Bonds[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 559-573.

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图/表 21

图式1. EDA复合物的概念及EDA复合物驱动的胺N-α位的活化模式

Scheme 1. Concepts of EDA complexes and activation patterns of amine N-α position driven by EDA complexes

图式2. 吡咯与芳基碘鎓盐的EDA复合物促进吡咯的直接芳基化

Scheme 2. Direct arylation of pyrrole promoted by EDA complexes of pyrrole with aryliodonium salt

图式3. N-杂芳烃与芳基重氮盐的EDA复合物促进N-杂芳烃的芳基化

Scheme 3. Arylation of N-heteroaromatics promoted by EDA complexes of N-heteroaromatics with aryl diazonium salts

图式4. 吲唑与芳基重氮盐的EDA复合物促进吲唑的芳基化

Scheme 4. Arylation of indazoles promoted by EDA complexes of indolizines with aryl diazonium salts

图式5. EDA复合物驱动的吲嗪与萘醌的偶联

Scheme 5. EDA complex-driven coupling of indolizine with naphthoquinone

图式6. EDA复合物驱动的吲哚与苄溴或α-溴代苯乙酮的脱卤偶联

Scheme 6. EDA complex-driven dehalogenation coupling of indoles with benzyl bromide or α-bromoacetophenone

图式7. N-杂芳烃与NHPI的EDA复合物促进N-杂芳烃烷基化

Scheme 7. Alkylation of N-heteroaromatic promoted by EDA complexes of N-heteroaromatics with NHPI

图式8. N-杂芳烃参与的EDA复合物促进未活化烯烃的双官能化

Scheme 8. Difunctionalization of unactivated olefins promoted by EDA complexes involving N-heteroaromatics

图式9. EDA复合物驱动喹喔啉酮与芳基叔胺的偶联

Scheme 9. EDA complex-driven coupling of quinoxalinones with aryl tertiary amines

图式10. 三级胺与对苯二腈的EDA复合物促进叔胺N-α C(sp3)—H芳基化

Scheme 10. N-α C(sp3)—H arylation of tertiary amines promoted by EDA complexes of tertiary amines with terephthalonitrile

图式11. 芳基叔胺与马来酰亚胺的EDA复合物促进芳基叔胺直接合成四氢喹啉

Scheme 11. Synthesis of tetrahydroquinoline promoted by EDA complexes of aryl tertiary amines with maleimides

图式12. 芳基叔胺与缺电子烯烃的EDA复合物促进四氢喹啉的合成

Scheme 12. Synthesis of tetrahydroquinolines promoted by EDA complexes of aryl tertiary amines with electron-deficient olefins

图式13. THIQs与烯丙基溴的EDA复合物促进叔胺N-α C(sp3)—H的烷基化

Scheme 13. N-α C(sp3)—H alkylation of THIQs promoted by EDA complexes of THIQs with allyl bromide

图式14. 四氢异喹啉与TCNHPI的EDA复合物促进THIQ N-α的烷基化

Scheme 14. N-α alkylation of THIQs promoted by EDA complexes of THIQs with TCNHPI

图式15. DPI/烷基硼酸为受体的EDA复合物促进THIQs N-α位的烷基化

Scheme 15. N-α alkylation of THIQs promoted by EDA complexes with DPI/alkylboronic acids as receptors

图式16. 苯甲酰腈/三价碘试剂为受体的EDA复合物促进叔胺N-α位的氰基化

Scheme 16. N-α cyanation of tertiary amines promoted by EDA complexes with benzoyl cyanide/trivalent iodine as receptor

图式17. 芳基叔胺与三价碘试剂的EDA复合物促进芳胺直接合成二氢吲哚

Scheme 17. Synthesis of dihydroindoles promoted by EDA complexes of aryl tertiary amines with trivalent iodine reagents

图式18. 吲哚与吡啶N-叶立德的EDA复合物促进吲哚C-2位直接胺化

Scheme 18. Amination of indoles at the C-2 position promoted by EDA complexes of indoles with pyridine N-yeridines

图式19. EDA复合物驱动甘氨酸衍生物与环氧烷烃的[3＋2]环加成

Scheme 19. EDA complex-driven [3＋2] cycloaddition of glycine derivatives with epoxides

图式20. 甘氨酸衍生物与Katritzky盐的EDA复合物促进氨基酸及肽的N-α的烷基化

Scheme 20. N-α alkylation of amino acids and peptides promoted by EDA complexe of glycines with Katritzky salts

图式21. 甘氨酸衍生物与硫鎓盐的EDA复合物促进BCPs的芳基和烷基化

Scheme 21. Arylation and alkylation of BCPs promoted by EDA complexes of glycine derivatives with thiolium salts

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