单原子光催化有机合成研究进展

doi:10.6023/cjoc202407042

摘要/Abstract

单原子光催化剂具有高表面积、优异的催化活性和选择性, 有助于提高反应效率并减少副反应的产生, 其催化机理易于理解, 在有机合成反应中展现出独特的潜力. 此外, 单原子光催化还具有优异的可回收利用性能, 是一种新颖的绿色催化策略, 为有机光催化合成化学提供独特的机会. 尽管单原子光催化在多个领域中均已获得广泛关注, 但在有机合成研究领域中的应用仍较少, 且缺乏系统性总结. 为了能够快速了解该研究领域的进展, 根据成键类型[C—C键和C—X (X=N, O, S, P, B等)键]系统性地综述了近十年来单原子光催化在有机合成应用中的进展. 此外, 对底物范围和机理进行了讨论, 旨在为开发新的单原子光催化有机合成方法奠定基础.

关键词: 单原子, 光催化, 有机合成

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

引用此文

吴利华, 杨建静, 闫克鲁, 许丽荣, 文江伟. 单原子光催化有机合成研究进展[J]. 有机化学, 2025, 45(5): 1591-1613.

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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图/表 56

图1. 单原子光催化剂论文统计

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

图2. 单原子光催化剂应用统计分析

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

图3. (A) HAADF-STEM图像和(B) CN和NiSAC/CN的紫外可见光谱

图式1. 芳基溴化物和胺偶联的底物范围

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

图式2. 可能的反应机理

Scheme 2. Proposed reaction mechanism

图4. (A) CdS-Pd的HAADF-STEM图像和(B) CdS和CdS-Pd的紫外光谱

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

表1. 光催化胺与醇的N-烷基化反应

Table 1. Photocatalytic N-alkylation of amines with alcohols

图式3. 光催化胺与醇的N-烷基化反应机理

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

图5. (A) Ag/g-C3N4的TEM图像和(B) g-C3N4、块状g-C3N4、Ag NPs和Ag/g-C3N4复合材料的紫外光谱

图式4. Ag/g-C3N4催化芳香醛和胺氧化酰胺化

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

图式5. Ag/g-C3N4催化杂芳醛和吡咯烷的氧化酰胺化

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

图式6. (A)光催化四氢呋喃的氧化机理和(B)可见光照射下Ag/g-C3N4表面的电子转移

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

图式7. Ag/g-C3N4在可见光下催化四氢呋喃中醛类和胺类氧化酰胺化的可能机理

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

图式8. AgPd@g-C3N4催化硝基芳烃的N-甲酰化反应

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

图6. Ni-mpg-CNx的结构

Figure 6. Structure of Ni-mpg-CNx

图式9. 光催化胺化的底物范围

Scheme 9. Substrate scope of photocatalytic amination

图式10. 光催化醇与胺交叉偶联的底物范围

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

图式11. Ni1-mpg-CN18催化醇与胺交叉偶联机理

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

图式12. 光催化醇与芳基卤代物交叉偶联的底物范围

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

图式13. 推测的机制

Scheme 13. Proposed mechanism

图式14. 光催化C—O交叉偶联的的底物范围

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

图式15. 醇胺交叉偶联的光催化范围

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

图式16. CoP@POC的合成示意图和结构

Scheme 16. Synthesis diagram and structure of CoP@POC

图式17. 苄胺偶联的底物范围

Scheme 17. Substrate range for coupling of benzylamines

图式18. 苄胺偶联的反应机理

Scheme 18. Reaction mechanism of coupling of benzylamines

图式19. 光促进AgF催化碘化物与苯的交叉偶联

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

图式20. 卤化物与芳香族化合物的交叉偶联

Scheme 20. Cross-coupling of halides with aromatic compounds

图式21. CoSA-N/NC的合成方法

Scheme 21. Synthesis method of CoSA-N/NC

图式22. 底物范围

Scheme 22. Substrate scope

图式23. 可能的机制

Scheme 23. Plausible mechanism

图7. (A) Pd1/C3N4高角环形暗场像-扫描透射电子显微镜图像和(B) C3N4, Pd1/C3N4和PdNP/C3N4紫外可见光谱

图式24. 底物范围

Scheme 24. Substrate scope

图式25. α-氨基砜的合成

Scheme 25. Synthesis of α-amidosulfones

图式26. β-丙酰氨基砜的合成

Scheme 26. Synthesis of β-propionamidosulfones

图式27. 推测的反应机理

Scheme 27. Postulated reaction mechanism

图8. CNH光催化剂示意图

Figure 8. Schematic representation of the CNH photocatalyst

图式28. 烯烃的范围

Scheme 28. Scope of alkenes

图式29. 亚磺酸的范围

Scheme 29. Scope of sulfinic acids

图式30. 假设的反应途径

Scheme 30. Postulated reaction pathway

图式31. 材料的合成示意图

Scheme 31. Schematic presentation of the synthesis of the materials

图9. (A) Ag(0)/Mg(OH)2的高角环形暗场像差校正图像和(B) Ag (0)/Mg(OH)2和Mg(OH)2的紫外吸收光谱

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.

图式32. AgEG/Mg(OH)2光催化硼化反应的结果

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

图式33. 光催化卤化物硼化反应的范围

Scheme 33. Scope of the photocatalytic borylation of alkyl halides

图10. Cu1/CN的合成方法

图11. (A) Cu1/CN的AC HAADF-STEM图像; (B) Cu1/CN的紫外吸收光谱

图式34. 烯烃的范围

Scheme 34. Scope of alkenes

图12. Ru1/CdS SACs的制备说明

图式35. 乳酸为模型底物的光催化胺化反应示意图

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

表2. Ru SAs/N-C和Ru纳米簇/C对喹啉选择性加氢的催化性能

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

图13. Ru SAs/N-C催化的各种喹啉加氢反应

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

图式36. 芳香族醇的选择性氧化

Scheme 36. Selective oxidation of aromatic alcohols

图14. PAN/Ag纳米和g-C3N4的合成示意图

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	—	—	—

表3. PAN/Ag NPs/g-C3N4催化烯烃的选择性转化a

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

图式37. PAN/Ag NPs/g-C3N4 NFs催化CH2 (C—H)选择性氧化的底物范围

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

图式38. 各种芳香卤化物的脱卤

Scheme 38. Dehalogenation of various aromatic halides

图式39. AgF/可见光系统介导的碘化物脱碘质子化

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

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