三芳胺在光催化反应中的研究进展

doi:10.6023/cjoc202408009

摘要/Abstract

光化学反应不仅利用可再生的光能作为能源, 而且可以发现一些传统热化学反应难以实现的反应历程, 成为近年来合成化学领域研究的热点. 光化学反应往往需要加入光催化剂吸收光子的能量, 进而与底物发生电子转移或能量转移来完成后续化学转化, 因此设计发展廉价易得、转化效率高和稳定性好的光敏剂是有机光化学反应的一项重要研究内容, 其中三芳胺在光催化反应中逐渐引起关注. 此综述对近年来通过三芳胺介导/催化的光化学反应研究进展进行了归纳总结, 阐述了可见光条件下三芳胺促进的芳烃碳氢键官能团化反应、烯烃官能团化反应和环加成反应. 最后对三芳胺在光催化反应中的应用进行了总结与展望.

关键词: 电子供体-受体复合物, 三芳胺, 自由基反应, 光化学反应, 三氟甲基

Photochemical reactions not only utilize renewable light energy as a source, but also can uncover reaction pathways that are difficult to achieve through traditional thermochemical reactions, making them an emerging research topic in the field of synthetic chemistry in recent years. Photochemical reactions often require the addition of a photocatalyst to absorb the energy of photons, and then undergo electron transfer or energy transfer with the substrate to complete the subsequent chemical transformation. Therefore, the design and development of inexpensive, easily accessible, high-efficiency, and stable photosensitizers is an important research topic in organic photochemical reactions. In this context, triarylamine has gradually attracted increasing attention in photocatalytic reactions. The recent research progress on photochemical reactions mediated/catalyzed by triarylamine is summarized. The content includes triarylamine-promoted functionalization of aromatic C—H bonds, olefin functionalization reactions, and cycloaddition reactions under visible light irradiation. Finally, the application of triarylamine in photocatalytic reactions is summarized and prospected.

Key words: electron donor-acceptor complex, triarylamine, radical reaction, photochemical reaction, trifluoromethyl group

引用此文

吴昊岩, 赫明月, 马军安, 张发光. 三芳胺在光催化反应中的研究进展[J]. 有机化学, 2025, 45(5): 1634-1643.

Haoyan Wu, Mingyue He, Jun'an Ma, Faguang Zhang. Recent Advances in Photochemical Reactions Enabled by Triarylamine[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1634-1643.

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图/表 9

图1. 三芳基自由基铵正离子作为单电子氧化剂

Figure 1. Triarylaminium radical cation as stoichiometric single-electron oxidants

图式1. 三芳胺-EDA体系催化的光化学反应

Scheme 1. Triarylamine-EDA-catalyzed photochemical reactions

图式2. 三芳胺-EDA体系催化的芳基碘苯脱卤芳基化反应

Scheme 2. Triarylamine-EDA-catalyzed dehalogenation arylation reaction of aryl halides with arenes

图式3. 三芳胺-EDA体系催化的芳烃C—H键烷基化反应与氰基化反应

Scheme 3. Triarylamine-EDA-catalyzed arene C—H alkylation reaction and cyanation reaction

图式4. 三芳胺催化的芳烃氟烷基化反应

Scheme 4. Fluoroalkylation of aromatic hydrocarbons catalyzed by triarylamine

图式5. 三芳胺催化苯酚氧化交叉偶联反应

Scheme 5. Triarylamine-catalyzed dehydrogenative cross-coupling of phenols

图式6. 三芳胺催化的烯烃磺酰化反应

Scheme 6. Triarylamine-catalyzed sulfonylation reactions of alkenes under visible light

图式7. 三芳胺催化的可见光烯烃双官能团化反应

Scheme 7. Triarylamine-catalyzed alkene difunctionalization under visible light

图式8. 三芳胺催化的环加成反应

Scheme 8. Cycloaddition catalyzed by triarylamine

参考文献 50

[1]	Beeson T. D.; Mastracchio A.; Hong J.-B.; Ashton K.; MacMillan D. W. C. Science 2007, 316, 582.
[2]	Narayanam J. M. R.; Stephenson C. R. J. Chem. Soc. Rev. 2011, 40, 102. doi: 10.1039/b913880n pmid: 20532341
[3]	Schultz D. M.; Yoon T. P. Science 2014, 343, 1239176.
[4]	Chen Y.; Lu L.-Q.; Yu D.-G.; Zhu C.-J.; Xiao W.-J. Sci. China, Chem. 2019, 62, 24.
[5]	Yu X.-Y.; Chen J.-R.; Xiao W.-J. Chem. Rev. 2021, 121, 506.
[6]	Xuan J.; Xiao W.-J. Angew. Chem., Int. Ed. 2012, 51, 6828.
[7]	Prier C. K.; Rankic D. A.; MacMillan D. W. C. Chem. Rev. 2013, 113, 5322.
[8]	Romero N. A.; Nicewicz D. A. Chem. Rev. 2016, 116, 10075.
[9]	Esposti A. D.; Fattori V.; Sabatini C.; Casalbore-Micelia G.; Marconia G. Phys. Chem. Chem. Phys. 2005, 7, 3738.
[10]	Shirota Y.; Kageyama H. Chem. Rev. 2007, 107, 953.
[11]	Cias P.; Slugovc C.; Gescheidt G. J. Phys. Chem. A 2011, 115, 14519.
[12]	Blanchard P.; Malacrida C.; Cabanetos C.; Roncali J.; Ludwigs S. Polym. Int. 2019, 68, 589. doi: 10.1002/pi.5695
[13]	Wang J.; Liu K.; Ma L.; Zhan X. Chem. Rev. 2016, 116, 14675.
[14]	Ji X. Synthesis 2016, 48, 18.
[15]	Hu J.; Wang J.; Nguyen T. H.; Zheng N. Beilstein J. Org. Chem. 2013, 9, 1977.
[16]	Marquez C. A.; Wang H.; Fabbretti F.; Metzger J. O. J. Am. Chem. Soc. 2008, 130, 17208. doi: 10.1021/ja806791c pmid: 19049280
[17]	Liu J.; Liu F.; Zhu Y.; Ma X.; Jia X. Org. Lett. 2015, 17, 1409.
[18]	Barham J. P.; John M. P.; Murphy J. A. J. Am. Chem. Soc. 2016, 138, 15482.
[19]	Zhang J.; Paladugu S. R.; Gillard R. M.; Sarkar A.; Boger D. L. J. Am. Chem. Soc. 2022, 144, 495.
[20]	Yuan Y.; Zhang S.; Sun Z.; Su Y.; Ma Q.; Yuan Y.; Jia X. Org. Lett. 2020, 22, 6294. doi: 10.1021/acs.orglett.0c02054 pmid: 32806190
[21]	Liu S.; Klussmann M. Org. Chem. Front. 2021, 8, 2932.
[22]	Lima C. G. S.; Lima T. Duarte M.; Jurberg I. D.; Paixão M. W. ACS Catal. 2016, 6, 1389.
[23]	Crisenza G. E.; Crisenza M.; Mazzarella D.; Melchiorre P. J. Am. Chem. Soc. 2020, 142, 5461. doi: 10.1021/jacs.0c01416 pmid: 32134647
[24]	Sumida Y.; Ohmiya H. Chem. Soc. Rev. 2021, 50, 6320. doi: 10.1039/d1cs00262g pmid: 33889895
[25]	Yang Z.; Liu Y.; Cao K.; Zhang X.; Jiang H.; Li J. Beilstein J. Org. Chem. 2021, 17, 771.
[26]	Wortman A. K.; Stephenson C. R. J. Chem 2023, 9, 2390. doi: 10.1016/j.chempr.2023.06.013 pmid: 37873033
[27]	Guo G.; Li X.; Ma J.; Shi Y.; Lv J.; Yang D. Chin. Chem. Lett. 2024, 35, 110024.
[28]	Sun K.; Shi A.; Liu Y.; Chen X.; Xiang P.; Wang X.; Qu L.; Yu B. Chem. Sci. 2022, 13, 5659.
[29]	Wu J.; Grant P. S.; Li X.; Noble A.; Aggarwal V. K. Angew. Chem., Int. Ed. 2019, 58, 5697.
[30]	Fu M.-C.; Shang R.; Zhao B.; Wang B.; Fu Y. Science 2019, 363, 1429.
[31]	de Pedro Beato, E.;Spinnato, D.; Zhou, W.; Melchiorre, P. J. Am. Chem. Soc. 2021, 143, 12304.
[32]	Wang L.; Byun J.; Li R.; Huang W.; Zhang K. A. I. Adv. Synth. Catal. 2018, 360, 4312.
[33]	Tasnim T.; Ayodele M. J.; Pitre S. P. J. Org. Chem. 2022, 87, 10555.
[34]	Dewanji A.; van Dalsen L.; Rossi-Ashton J. A.; Gasson E.; Crisenza G. E. M.; Procter D. J. Nat. Chem. 2023, 15, 43.
[35]	Castillo-Pazos D, J.; Lasso J. D.; Hamzehpoor E.; Ramos- Sánchez J.; Salgado J. M.; Cosa G.; Perepichka D. F.; Li C.-J. Chem. Sci. 2023, 14, 3470. doi: 10.1039/d2sc07078b pmid: 37006691
[36]	Kato N.; Nanjo T.; Takemoto Y. Chem. Pharm. Bull. 2023, 71, 747.
[37]	Lasso J. D.; Castillo-Pazos D. J.; Salgado J. M.; Ruchlin C.; Lefebvre L.; Farajat D.; Perepichka D. F.; Li C.-J. J. Am. Chem. Soc. 2024, 146, 2583. doi: 10.1021/jacs.3c11225 pmid: 38232387
[38]	Koike T.; Akita M. Chem 2018, 4, 409.
[39]	Wu H.-Y.; Tang X.; Guo R.; Ang H. T.; Nie J.; Wu J.; Ma J.-A.; Zhang F.-G. Cell Rep. Phys. Sci. 2024, 5, 102135.
[40]	Zeng J.; Xu Z.; Ma J.-A. Chin. J. Org. Chem. 2020, 40, 1105 (in Chinese).
	(曾俊良, 许志红, 马军安, 有机化学, 2020, 40, 1105.) doi: 10.6023/cjoc201912024
[41]	Mykhailiuk P. K. Angew. Chem., Int. Ed. 2015, 54, 6558.
[42]	Zhai S.-J.; Cahard D.; Zhang F.-G.; Ma J.-A. Chin. Chem. Lett. 2022, 33, 863.
[43]	Gao C.-F.; Zhou Y.; Ma H.; Zhang Y.; Nie J.; Zhang F.-G.; Ma J.-A. CCS Chem. 2022, 4, 3693.
[44]	Tang X.; He M.-Y.; Guo R.; Liu H.-N.; Nie J.; Marek I.; Ma J.-A.; Zhang F.-G. CCS Chem. 2024, 6, 2825.
[45]	Zeng J.-L.; Chen Z.; Zhang F.-G.; Ma J.-A. Org. Lett. 2018, 20, 4562.
[46]	He M.-Y.; Tang X.; Wu H.-Y.; Nie J.; Ma J.-A.; Zhang F.-G. Org. Lett. 2023, 25, 9041.
[47]	Xie Y.; Xuan J. Chin. J. Org. Chem. 2022, 42, 4247 (in Chinese).
	(谢阳, 宣俊, 有机化学, 2022, 42, 4247.) doi: 10.6023/cjoc202207016
[48]	Li S.; Zhou L. Chin. J. Org. Chem. 2022, 42, 3944 (in Chinese).
	(李森, 周磊, 有机化学, 2022, 42, 3944.) doi: 10.6023/cjoc202206058
[49]	Discekici E. H.; Treat N. J.; Poelma S. O.; Mattson K. M.; Hudson Z. M.; Luo Y.; Hawker C. J.; Read de Alaniz J. Chem. Commun. 2015, 51, 11705.
[50]	Speck F.; Rombach D.; Wagenknecht H.-A. Beilstein J. Org. Chem. 2019, 15, 52.