Electron Donor-Acceptor (EDA) Complex-Driven Activation of N-α C—H Bonds

doi:10.6023/cjoc202406050

Abstract

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

Cite this article

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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Fig. & Tab. 21

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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电子供体-受体(EDA)复合物驱动的N-α位C—H键活化