水溶性光催化剂介导的水相反应研究进展

doi:10.6023/cjoc202407046

摘要/Abstract

可见光光催化剂具有将光能转化为化学能的特点, 为在温和条件下实现化学转化开辟了新的途径. 水作为一种安全、廉价、清洁、丰富的反应介质, 将其应用于有机化学反应能够有效地减少环境污染. 可见光光催化剂和水的结合是发展绿色可持续化学目标之一, 可见光介导的水相反应综合了二者的优点, 有望更好地发挥“绿色化学”理念. 由于大多数有机底物和催化剂在水中的溶解性差, 近年来发展了一些水溶性可见光光催化剂用于有机转化. 此外, 水溶性提升了催化剂的生物兼容性, 进而提高实用性, 将应用扩展至生物领域. 基于此, 本综述总结了近年来报道的水溶性光催化剂, 并依据水溶性光催化体系的不同, 分为水溶性金属、有机小分子和超分子光催化剂三类进行综述.

关键词: 水溶性光催化剂, 水介质, 可见光, 水相反应

Visible-light photocatalysts are capable of converting light energy into chemical energy, which opens a new way to achieve chemical transformations under mild conditions. As a safe, cheap, clean and abundant reaction medium, the appli- cation of water in organic synthesis can effectively reduce environmental pollution. In this regard, the combined use of visible-light photocatalysts and water meets the goal for the development of green and sustainable chemistry. Given the poor solubility of most organic substrates and catalysts in water, a number of water-soluble visible-light photocatalysts have been developed for organic transformations in recent years. In addition, water solubility makes visible-light photocatalyst biocompatible, which improves the practicality and extends the application in biological field. In this regard, the review provides a summary of water-soluble photocatalysts reported in recent years, which are categorized into metal, organic and supramolecular water-soluble photocatalysts based on different catalytic systems.

Key words: water-soluble photocatalysts, water medium, visible light, aqueous reactions

引用此文

吴凌苇, 崔浩, 张霄. 水溶性光催化剂介导的水相反应研究进展[J]. 有机化学, 2025, 45(4): 1097-1118.

Lingwei Wu, Hao Cui, Xiao Zhang. Recent Advances in Water-Soluble Photocatalysts-Mediated Aqueous Reactions[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1097-1118.

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图/表 29

图式1. 构建水溶性光催化剂的策略

Scheme 1. Strategies for constructing water-soluble photocatalysts

图式2. 常用的金属铱配合物

Scheme 2. Commonly used iridium complexes

图式3. PQS-attached-[Ir]的设计

Scheme 3. Design of PQS-attached-[Ir]

图式4. 可见光诱导的烯烃双官能化反应、烯醇乙酸酯和烯胺磺酰化反应

Scheme 4. Visible light-induced difunctionalization of alkenes, enol acetates, and enamide sulfonylation

图式5. 可见光诱导的亚胺还原反应

Scheme 5. Visible light-induced reduction of imines

图式6. Irsppy和其他光催化剂的催化性能比较

Scheme 6. Comparison of catalytic performance between Irsppy and other photocatalysts

图式7. Irsppy在还原反应中的应用

Scheme 7. Application of Irsppy in reduction reactions

图式8. Irsppy在不同光强下的作用机制

Scheme 8. Action modes of Irsppy under different light intensities

图式9. Irsppy在不同光强下的反应

Scheme 9. Rreactions using Irsppy under different light intensities

图式10. 可见光诱导的乳酸链球菌肽的脱氢丙氨酸修饰反应

Scheme 10. Visible light-induced dehydroalanine modification of nisin

图式11. 可见光诱导的二肽的三氟甲基化反应

Scheme 11. Visible light-induced trifluoromethylation of dipeptide

图式12. 常用的金属钌配合物

Scheme 12. Commonly used ruthenium complexes

图式13. 可见光诱导的N-杂芳烃的自由基芳基化反应

Scheme 13. Visible light-induced radical arylation of N-heteroaromatics

图式14. 可见光诱导的N-杂环氧化脱氢反应

Scheme 14. Visible light-induced oxidative dehydrogenation of N-heterocycles

图式15. 可见光诱导的N-杂环氧化脱氢反应的机理

Scheme 15. Mechanism of visible light-induced oxidative dehydrogenation of N-heterocycles

图式16. 可见光诱导的全氟烷基碘化物的自由基加成反应

Scheme 16. Visible light-induced radical addition reaction of perfluoroalkyl iodides

图式17. 可见光诱导的芳香醛的氧化酰胺化反应

Scheme 17. Visible light-induced oxidative amidation of aromatic aldehydes

图式18. 可见光诱导的脱羧羟基化反应

Scheme 18. Visible light-induced decarboxylative hydroxylation reaction

图式19. 用于合成H2O2的水溶性光催化剂

Scheme 19. Water-soluble photocatalysts for the synthesis of H2O2

图式20. 可见光诱导的蛋白质-聚合物偶联物(PPC)的合成

Scheme 20. Visible light-induced synthesis of protein-polymer conjugates (PPC)

图式21. PET-RAFT聚合的机理

Scheme 21. Mechanism of PET-RAFT polymerization

图式22. 可见光诱导4P-DPAIPN和Co(oTMPyP)催化的CO2还原

Scheme 22. Visible light-induced 4P-DPAIPN and Co(oTMPyP)-catalyzed reduction of CO2

图式23. 可见光诱导的芳基硼酸有氧氧化羟基化反应

Scheme 23. Visible light-induced aerobic oxidative hydroxylation of arylboronic acids

图式24. 可见光诱导四氟硼酸芳基重氮盐和吡啶盐酸盐的偶联反应

Scheme 24. Visible light-induced coupling reaction of aryl diazonium salts of tetrafluoroborate and pyridine hydrochloride

图式25. 可见光诱导的氢化偶氮苯、烯烃和氢化硅烷的氧化反应

Scheme 25. Visible light-induced oxidative reaction of hydrazo- benzenes, olefins and hydrosilanes

图式26. 可见光诱导芳基/烷基硫化物的选择性空气氧化

Scheme 26. Visible light-induced selective aerial oxidation of aryl/alkyl sulfides

图式27. 可见光诱导的频哪醇偶联反应

Scheme 27. Visible light-induced pinacol coupling reaction

图式28. 可见光诱导的CO2还原

Scheme 28. Visible light-induced reduction of CO2

图式29. 可见光诱导芳基/烷基硫化物的选择性空气氧化

Scheme 29. Visible light-induced selective aerobic oxidation of aryl/alkyl sulfides

参考文献 53

[1]	(a) Nicolaou, K. C. Isr. J. Chem. 2018, 58, 104.
	(b) Wang, J.; Wang, Z.; He, W.; Ye, L. Chin. J. Org. Chem. 2024, 44, 1786 (in Chinese).
	(王家晟, 王泽树, 何卫民, 叶龙武, 有机化学, 2024, 44, 1786.) doi: 10.6023/cjoc202401010
[2]	Sheldon, R. A. Green Chem. 2005, 7, 267.
[3]	(a) Li, C.-J. Chem. Rev. 1993, 93, 2023.
	(b) Li, C.-J. Chem. Rev. 2005, 105, 3095.
	(c) Simon, M.-O.; Li, C.-J. Chem. Soc. Rev. 2012, 41, 1415.
	(d) Javaherian, M.; Movaheditabar, P. J. Iran. Chem. Soc. 2023, 20, 2103.
[4]	Rideout, D. C.; Breslow, R. J. Am. Chem. Soc. 1980, 102, 7816.
[5]	(a) Ciamician, G. Science 1912, 36, 385. pmid: 17836492
	(b) Yoon, T. P.; Ischay, M. A.; Du, J. Nat. Chem. 2010, 2, 527. pmid: 17836492
	(c) Shaw, M. H.; Twilton, J.; MacMillan, D. W. C. J. Org. Chem. 2016, 81, 6898. pmid: 17836492
	(d) Cai, B.; Xuan, J. Chin. J. Org. Chem. 2021, 41, 4565 (in Chinese). pmid: 17836492
	(蔡宝贵, 宣俊, 有机化学, 2021, 41, 4565.) doi: 10.6023/cjoc202109040 pmid: 17836492
	(e) Su, Y.; Zou, Y.; Xiao, W. Chin. J. Org. Chem. 2022, 42, 3201 (in Chinese). pmid: 17836492
	(苏艺雯, 邹有全, 肖文精, 有机化学, 2022, 42, 3201.) doi: 10.6023/cjoc202207046 pmid: 17836492
	(f) Holmberg-Douglas, N.; Nicewicz, D. A. Chem. Rev. 2022, 122, 1925. pmid: 17836492
[6]	(a) Vega-Peñaloza, A.; Mateos, J.; Companyó, X.; Escudero-Casao, M.; Dell'Amico, L. Angew. Chem., Int. Ed. 2021, 60, 1082.
	(b) Lee, Y.; Kwon, M. S. Eur. J. Org. Chem. 2020, 2020, 6028.
	(c) Romero, N. A.; Nicewicz, D. A. Chem. Rev. 2016, 116, 10075.
[7]	(a) Li, L.; Huang, M.; Liu, C.; Xiao, J.-C.; Chen, Q.-Y.; Guo, Y.; Zhao, Z.-G. Org. Lett. 2015, 17, 4714. pmid: 21381734
	(b) Nguyen, J. D.; Tucker, J. W.; Konieczynska, M. D.; Stephenson, C. R. J. J. Am. Chem. Soc. 2011, 133, 4160. doi: 10.1021/ja108560e pmid: 21381734
	(c) Yajima, T.; Ikegami, M. Eur. J. Org. Chem. 2017, 2017, 2126. pmid: 21381734
	(d) Prasad Hari, D.; Hering, T.; König, B. Angew. Chem., Int. Ed. 2014, 53, 725. pmid: 21381734
[8]	Jeyapalan, V.; Varadharajan, R.; Veerakanellore, G. B.; Ramamurthy, V. J. Photochem. Photobiol. A: Chem. 2021, 420, 113492.
[9]	Tucker, J. W.; Stephenson, C. R. J. J. Org. Chem. 2012, 77, 1617.
[10]	(a) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322.
	(b) Chan, A. Y.; Perry, I. B.; Bissonnette, N. B.; Buksh, B. F.; Edwards, G. A.; Frye, L. I.; Garry, O. L.; Lavagnino, M. N.; Li, B. X.; Liang, Y.; Mao, E.; Millet, A.; Oakley, J. V.; Reed, N. L.; Sakai, H. A.; Seath, C. P.; MacMillan, D. W. C. Chem. Rev. 2022, 122, 1485.
[11]	(a) Schwarz, J. L.; Schäfers, F.; Tlahuext-Aca, A.; Lückemeier, L.; Glorius, F. J. Am. Chem. Soc. 2018, 140, 12705. doi: 10.1021/jacs.8b08052 pmid: 33163257
	(b) Ganley, J. M.; Murray, P. R. D.; Knowles, R. R. ACS Catal. 2020, 10, 11712. doi: 10.1021/acscatal.0c03567 pmid: 33163257
[12]	Bu, M.; Cai, C.; Gallou, F.; Lipshutz, B. H. Green Chem. 2018, 20, 1233.
[13]	Shen, T.; Zhou, S.; Ruan, J.; Chen, X.; Liu, X.; Ge, X.; Qian, C. Adv. Colloid Interface Sci. 2021, 287, 102299.
[14]	Guo, X.; Okamoto, Y.; Schreier, M. R.; Ward, T. R.; Wenger, O. S. Chem. Sci. 2018, 9, 5052.
[15]	Kerzig, C.; Guo, X.; Wenger, O. S. J. Am. Chem. Soc. 2019, 141, 2122.
[16]	Zhao, Y.; Zhang, C.; Chu, L.; Zhou, Q.; Huang, B.; Ji, R.; Zhou, X.; Zhang, Y. Water Res. 2022, 225, 119212.
[17]	Kerzig, C.; Wenger, O. S. Chem. Sci. 2019, 10, 11023.
[18]	van Lier, R. C. W.; de Bruijn, A. D.; Roelfes, G. Chem.-Eur. J. 2021, 27, 1430.
[19]	Nguyen, T.-T. H.; O’Brien, C. J.; Tran, M. L. N.; Olson, S. H.; Settineri, N. S.; Prusiner, S. B.; Paras, N. A.; Conrad, J. Org. Lett. 2021, 23, 3823.
[20]	Zhou, Y.; Wang, J.; Gu, Z.; Wang, S.; Zhu, W.; Aceña, J. L.; Soloshonok, V. A.; Izawa, K.; Liu, H. Chem. Rev. 2016, 116, 422. doi: 10.1021/acs.chemrev.5b00392 pmid: 26756377
[21]	Xue, D.; Jia, Z.-H.; Zhao, C.-J.; Zhang, Y.-Y.; Wang, C.; Xiao, J. Chem.-Eur. J. 2014, 20, 2960.
[22]	(a) Yalazan, H.; Akkol, C.; Saka, E. T.; Kantekin, H. Appl. Organomet. Chem. 2023, 37, e6975. pmid: 34257312
	(b) Li, Z.; Wang, J.-W.; Huang, Y.; Ouyang, G. Chin. J. Catal. 2023, 49, 160 (in Chinese). pmid: 34257312
	(李孜孜, 王嘉蔚, 黄衍钧, 欧阳钢锋, 催化学报, 2023, 49, 160.) doi: 10.1016/S1872-2067(23)64433-X pmid: 34257312
	(c) Wang, J.-W.; Jiang, L.; Huang, H.-H.; Han, Z.; Ouyang, G. Nat. Commun. 2021, 12, 4276. doi: 10.1038/s41467-021-24647-y pmid: 34257312
	(d) Kumar, A.; Prajapati, P. K.; Aathira, M. S.; Bansiwal, A.; Boukherroub, R.; Jain, S. L. J. Colloid Interface Sci. 2019, 543, 201. pmid: 34257312
[23]	Srinath, S.; Abinaya, R.; Prasanth, A.; Mariappan, M.; Sridhar, R.; Baskar, B. Green Chem. 2020, 22, 2575.
[24]	(a) Piechowska, P.; Zawirska-Wojtasiak, R.; Mildner-Szkudlarz, S. Nutrients 2019, 11, 814.
	(b) Luo, B.; Song, X. Eur. J. Med. Chem. 2021, 224, 113688.
[25]	(a) Hari, D. P.; König, B. Chem. Commun. 2014, 50, 6688.
	(b) Amos, S. G. E.; Garreau, M.; Buzzetti, L.; Waser, J. Beilstein J. Org. Chem. 2020, 16, 1163.
[26]	Yoshioka, E.; Kohtani, S.; Jichu, T.; Fukazawa, T.; Nagai, T.; Kawashima, A.; Takemoto, Y.; Miyabe, H. J. Org. Chem. 2016, 81, 7217. doi: 10.1021/acs.joc.6b01102 pmid: 27314306
[27]	You, G.; Wang, K.; Wang, X.; Wang, G.; Sun, J.; Duan, G.; Xia, C. Org. Lett. 2018, 20, 4005.
[28]	Wang, H.; Li, Y.; Tang, Z.; Wang, S.; Zhang, H.; Cong, H.; Lei, A. ACS Catal. 2018, 8, 10599.
[29]	Natarajan, P.; Chuskit, D.; Priya, P. Green Chem. 2019, 21, 4406. doi: 10.1039/c9gc01557d
[30]	Liu, J.; Yao, H.; Li, X.; Wu, H.; Lin, A.; Yao, H.; Xu, J.; Xu, S. Org. Chem. Front. 2020, 7, 1314.
[31]	(a) James, N. S.; Joshi, P.; Ohulchanskyy, T. Y.; Chen, Y.; Tabaczynski, W.; Durrani, F.; Shibata, M.; Pandey, R. K. Eur. J. Med. Chem. 2016, 122, 770.
	(b) Sun, C.; Du, W.; Wang, B.; Dong, B.; Wang, B. BMC Chem. 2020, 14, 21.
[32]	Deol, H.; Kumar, M.; Bhalla, V. RSC Adv. 2018, 8, 31237.
[33]	Cervantes-González, J.; Vosburg, D. A.; Mora-Rodriguez, S. E.; Vázquez, M. A.; Zepeda, L. G.; Gómez, C. V.; Lagunas-Rivera, S. ChemCatChem 2020, 12, 3811.
[34]	(a) Zhang, W.; Gacs, J.; Arends, I. W. C. E.; Hollmann, F. ChemCatChem 2017, 9, 3821. pmid: 32802571
	(b) Yuan, B.; Mahor, D.; Fei, Q.; Wever, R.; Alcalde, M.; Zhang, W.; Hollmann, F. ACS Catal. 2020, 10, 8277. doi: 10.1021/acscatal.0c01958 pmid: 32802571
[35]	Xu, J.; Arkin, M.; Peng, Y.; Xu, W.; Yu, H.; Lin, X.; Wu, Q. Green Chem. 2019, 21, 1907.
[36]	Nowak-Król, A.; Shoyama, K.; Stolte, M.; Würthner, F. Chem. Commun. 2018, 54, 13763.
[37]	Renner, R.; Stolte, M.; Heitmüller, J.; Brixner, T.; Lambert, C.; Würthner, F. Mater. Horiz. 2022, 9, 350.
[38]	Gryszel, M.; Rybakiewicz, R.; Głowacki, E. D. Adv. Sustainable Syst. 2019, 3, 1900027.
[39]	Gryszel, M.; Schlossarek, T.; Würthner, F.; Natali, M.; Głowacki, E. D. ChemPhotoChem 2023, 7, e202300070.
[40]	Shang, T.-Y.; Lu, L.-H.; Cao, Z.; Liu, Y.; He, W.-M.; Yu, B. Chem. Commun. 2019, 55, 5408.
[41]	(a) Olson, R. A.; Korpusik, A. B.; Sumerlin, B. S. Chem. Sci. 2020, 11, 5142.
	(b) Xu, J.; Jung, K.; Corrigan, N. A.; Boyer, C. Chem. Sci. 2014, 5, 3568.
[42]	Lee, Y.; Kwon, Y.; Kim, Y.; Yu, C.; Feng, S.; Park, J.; Doh, J.; Wannemacher, R.; Koo, B.; Gierschner, J.; Kwon, M. S. Adv. Mater. 2022, 34, 2108446.
[43]	Ma, F.; Luo, Z.-M.; Wang, J.-W.; Ouyang, G. J. Am. Chem. Soc. 2024, 146, 17773.
[44]	Singh, P. P.; Srivastava, V. Org. Biomol. Chem. 2021, 19, 313.
[45]	Chen, K.; Cheng, Y.; Chang, Y.; Li, E.; Xu, Q.-L.; Zhang, C.; Wen, X.; Sun, H. Tetrahedron 2018, 74, 483.
[46]	Xie, H.-Y.; Han, L.-S.; Huang, S.; Lei, X.; Cheng, Y.; Zhao, W.; Sun, H.; Wen, X.; Xu, Q.-L. J. Org. Chem. 2017, 82, 5236.
[47]	Tanioka, M.; Oyama, M.; Nakajima, K.; Mori, M.; Harada, M.; Matsuya, Y.; Kamino, S. Phys. Chem. Chem. Phys. 2024, 26, 4474. doi: 10.1039/d3cp05585j pmid: 38240132
[48]	Zhang, R.-Z.; Niu, K.-K.; Bi, Y.-S.; Liu, H.; Yu, S.-S.; Wang, Y.-B.; Xing, L.-B. Green Chem. 2024, 26, 2241.
[49]	(a) Yoshizawa, M.; Klosterman, J. K.; Fujita, M. Angew. Chem., Int. Ed. 2009, 48, 3418. pmid: 21863792
	(b) Chakrabarty, R.; Mukherjee, P. S.; Stang, P. J. Chem. Rev. 2011, 111, 6810. doi: 10.1021/cr200077m pmid: 21863792
	(c) Chen, L.; Chen, Q.; Wu, M.; Jiang, F.; Hong, M. Acc. Chem. Res. 2015, 48, 201. pmid: 21863792
	(d) Morimoto, M.; Bierschenk, S. M.; Xia, K. T.; Bergman, R. G.; Raymond, K. N.; Toste, F. D. Nat. Catal. 2020, 3, 969. pmid: 21863792
	(e) Mu, C.; Jian, S.; Zhang, M. Chem.-Eur. J. 2024, e202401264. pmid: 21863792
[50]	Zhang, Z.; Zhao, Z.; Hou, Y.; Wang, H.; Li, X.; He, G.; Zhang, M. Angew. Chem., Int. Ed. 2019, 58, 8862.
[51]	Noto, N.; Hyodo, Y.; Yoshizawa, M.; Koike, T.; Akita, M. ACS Catal. 2020, 10, 14283.
[52]	Ren, F.-Y.; Chen, K.; Qiu, L.-Q.; Chen, J.-M.; Darensbourg, D. J.; He, L.-N. Angew. Chem., Int. Ed. 2022, 61, e202200751.
[53]	Maitra, P. K.; Bhattacharyya, S.; Hickey, N.; Mukherjee, P. S. J. Am. Chem. Soc. 2024, 146, 15301.