Research Progress of Single-Atom Photocatalysis in Organic Synthesis

doi:10.6023/cjoc202407042

Abstract

The single atom photocatalyst exhibits a large surface area, exceptional catalytic activity, and selectivity, thereby enhancing reaction efficiency and minimizing the occurrence of side reactions. Its catalytic mechanism is easily comprehensible, rendering it uniquely promising for organic synthesis reactions. The single-atom photocatalysis, in addition to its excellent recyclability, represents a novel and environmentally friendly catalytic strategy that offers unique opportunities for organic photocatalytic synthesis chemistry. Although single-atom photocatalysis has received widespread attention in many fields, its application in organic synthesis research is still relatively rare and lacks a systematic summary. In order to enable readers to quickly understand the progress in this field, the present review provides a comprehensive overview of the applications of single atom photocatalysts in various organic synthesis reactions over the past decade, classified according to bond formation involving C—C and C—X (X=N, O, S, P, B, etc.). Moreover, this review also elucidates the application range and underlying mechanisms involved in these reactions, aiming to lay the foundation for the development of new single-atom photocatalytic organic synthesis methods.

Key words: single atom, photocatalysis, organic synthesis

Cite this article

Lihua Wu, Jianjing Yang, Kelu Yan, Lirong Xu, Jiangwei Wen. Research Progress of Single-Atom Photocatalysis in Organic Synthesis[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1591-1613.

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Fig. & Tab. 56

Figure 1. Single-atom photocatalyst papers statistics Data comes from Web of science search

Figure 2. Application and statistical analysis of single-atom photocatalyst Data comes from Web of science search

Scheme 1. Substrate scope for coupling of aryl bromides and amines

Scheme 2. Proposed reaction mechanism

Figure 4. (A) HAADF-STEM images of CdS-Pd, and (B) UV-Vis spectra for CdS and CdS-Pd SACs Copyright the 2022 American Chemical Society.

Entry	Alohols	Amines	Product	Amine	Yield/%
Entry	Alohols	Amines	Product	Amine	6	7
1				90	21	69
2				65	21	44
3				88	18	70
4				91	19	72
5				70	29	41
6				31	15	16
7				62	23	39
8				26	12	14
9				22	13	9

Table 1. Photocatalytic N-alkylation of amines with alcohols

Scheme 3. Mechanism of photocatalytic N-alkylation of amines with alcohols

Scheme 4. Oxidative amidation of aromatic aldehydes and amines catalyzed by Ag/g-C3N4

Scheme 5. Oxidative amidation of heteroaromatic aldehydes and pyrrolidine catalyzed by Ag/g-C3N4

Scheme 6. (A) Mechanism of photocatalytic oxidation of THF, and (B) Electron-transfer approach on Ag/g-C3N4 surface under visible light irradiation

Scheme 7. Plausible mechanism of the Ag/g-C3N4-catalyzed oxidative amidation of aldehydes and amines in THF under visible light irradiation.

Scheme 8. N-Formylation of nitroarenes catalysed by AgPd@- g-C3N4

Figure 6. Structure of Ni-mpg-CNx

Scheme 9. Substrate scope of photocatalytic amination

Scheme 10. Substrate scope for photocatalytic cross-coupling of alcohols and amines

Scheme 11. Mechanism of cross-coupling of alcohols and amines catalyzed by Ni1-mpg-CN18

Scheme 12. Substrate scope for the photocatalytic cross-coupling of alcohols with aryl halides

Scheme 13. Proposed mechanism

Scheme 14. Substrate scope for photocatalytic C—O cross-coupling

Scheme 15. Scope of the photocatalytic cross-coupling of alcohols and amines

Scheme 16. Synthesis diagram and structure of CoP@POC

Scheme 17. Substrate range for coupling of benzylamines

Scheme 18. Reaction mechanism of coupling of benzylamines

Scheme 19. Photopromoted AgF-catalyzed cross-coupling of iodide and benzene

Scheme 20. Cross-coupling of halides with aromatic compounds

Scheme 21. Synthesis method of CoSA-N/NC

Scheme 22. Substrate scope

Scheme 23. Plausible mechanism

Scheme 24. Substrate scope

Scheme 25. Synthesis of α-amidosulfones

Scheme 26. Synthesis of β-propionamidosulfones

Scheme 27. Postulated reaction mechanism

Figure 8. Schematic representation of the CNH photocatalyst

Scheme 28. Scope of alkenes

Scheme 29. Scope of sulfinic acids

Scheme 30. Postulated reaction pathway

Scheme 31. Schematic presentation of the synthesis of the materials

Figure 9. (A) High-angle annular dark field aberration corrected (HAADF AC)-STEM image of Ag(0)/Mg(OH)2, and (B) UV-vis spectra of Ag(0)/Mg(OH)2 and Mg(OH)2 Copyright Applied Catalysis B: Environmental 299 (2021) 120674.

Scheme 32. Outcome of the borylation reactions AgEG/Mg(OH)2 photocatalysis

Scheme 33. Scope of the photocatalytic borylation of alkyl halides

Scheme 34. Scope of alkenes

Scheme 35. Schematic diagram of photocatalytic amination using lactic acid as a model substrate

Entry	Catalysts	Conv./%	Selec./%
Entry	Catalysts	Conv./%	65	66	67
1	Ru SAs/N-C	>99	>99	<1	0
2	Ru SAs/C	>99	79	21	0

Table 2. Catalytic performance of Ru SAs/N-C and Ru nano- clusters/C for the selective hydrogenation of quinoline

Figure 13. Hydrogenation of various quinolines catalyzed by Ru SAs/N-C

Scheme 36. Selective oxidation of aromatic alcohols

Entry	Substrate	Conversion/%	Selectivity/%
Entry	Substrate	Conversion/%	71	72	73	74
1		98	60	32	1	7
2		98	65	25	—	10
3		97	62	34	—	4
4		81	54	40	2	4
5		72	50	35	5	10
6		65	45	—	—	—

Table 3. Selective conversion of olefins catalyzed by PAN/Ag NPs/g-C3N4

Scheme 37. Substrate scope of selective oxidation of CH2 (C—H) catalyzed by PAN/Ag NPs/g-C3N4 NFs

Scheme 38. Dehalogenation of various aromatic halides

Scheme 39. AgF/visible light system-mediated deiodination and protonation of iodide

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