Recent Progresses in P/N-Heteroleptic Cu(I)-Photocatalyst-Mediated Visible-Light-Driven Photocatalytic Reactions

doi:10.6023/cjoc202406018

Abstract

Visible-light-driven photocatalytic reactions have become one of hot research toptics in organic chemistry and catalytic chemistry since 2008. Among various photocatalytic reactions, the predominant tranistion-metal photocatalysts are those photosensitizers based on noble transition-metals, such as Ru(II) and Ir(III) as the central metal. However, this type of tranisition-metal photocatalysts has several drawbacks associated with their central metals including poor reserves in the earth, high prices and high toxicities. Recently, photocatalysts based on the earth-abundant copper(I) as the central metal have been continuously explored and gradually applied in photocatalytic reactions. In this regard, P/N-heteroleptic Cu(I)-photocatalyst- triggered photocatalytic reactions have specially received great attention and gained rapid development. Such Cu(I)- photocatalysts have advantages of abundant reserves, low prices and low toxicities related to their copper(I) central metal. These photocatalysts not only can replace Ru(II)- and Ir(III)-photocatalyts to trigger conventional photocatalytic reactions, but also can realize some photocatalytic reactions that are hard to be accomplished by Ru(II)- and Ir(III)-based photocatalysts, thus playing an important role in the highly efficient construction of molecular diversities. The recent progress in P/N-heteroleptic Cu(I)-photocatalyst-triggered visible-light-driven photocatalytic reactions is reviewed according to four catagories of different reaction mechanisms, namely, single electron transfer, bifunctional catalysis of Cu(I)-photocatalysts, copper/transition metal synergistic catalysis and energy transfer. At the end of this review, the problems and limitations in this field are summarized, and the future reasearch direction of this field is also prospected.

Key words: visible light, P/N-heteroleptic Cu(I) photocatalyst, photocatalytic reaction, earth-abundant metal

Cite this article

Sicheng Zhou, Yunkui Liu. Recent Progresses in P/N-Heteroleptic Cu(I)-Photocatalyst-Mediated Visible-Light-Driven Photocatalytic Reactions[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1644-1668.

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Fig. & Tab. 34

Figure 1. Representative photocatalysts

Scheme 1. Synthesis of P/N heteroleptic Cu(I)-photocatalysts and part of compound library

Scheme 2. Performance of P/N-heteroleptic Cu(I)-photocatalysts versus traditional noble-metal based photocatalysts in several photocatalytic reactions

Scheme 3. Two mechanistic modes of single electron transfer

Scheme 4. Borylation of aryl halides and desulfonation of sulfonamides catalyzed by P/N-heteroleptic Cu(I)-photocatalysts

Scheme 5. Synthesis of [5]helicene through P/N-heteroleptic Cu(I)-photocatalyst

Scheme 6. P/N heteroleptic Cu(I)-photocatalyst-catalyzed synthesis of carbazoles from triarylamines

Scheme 7. P/N-heteroleptic Cu(I)-photocatalyst-catalyzed synthesis of 1,3-diketones, alkyl bromides, cyclopenta[b]furan-2-ones and methyl 5-phenyl-1H-pyrrole-2-carboxylates

Scheme 8. P/N-heteroleptic Cu(I)-photocatalyst-catalyzed chlo- rotrifluoromethylation of olefins

Scheme 9. P/N-heteroleptic Cu(I)-photocatalyst-catalyzed chemoselective functionalization of C(sp3)—H bonds of N-alkoxyphtha- limides

Scheme 10. P/N-heteroleptic Cu(I)-photocatalyst-catalyzed Minsci radical coupling reaction between NHPI esters and azaarenes

Scheme 11. P/N-heteroleptic Cu(I)-photocatalyst-triggered domino radical cyclization of 1,n-enynes

Scheme 12. P/N-heteroleptic Cu(I)-photocatalyst-triggered polymerization reaction

Scheme 13. P/N-heteroleptic Cu(I)-photocatalys -catalyzed cross-dehydrogenation-coupling reaction

Scheme 14. P/N-heteroleptic Cu(I)-photocatalyst catalyzed photoreductive dehalogenation of organic halides

Scheme 15. P/N-heteroleptic Cu(I)-photocatalyst-catalyzed deoxygenative cross coupling between aromatic alkynes and alkyl aldehydes

Scheme 16. Cross coupling with aromatic alkynes enabled by P/N-heteroleptic Cu(I)-photocatalyst with tertiary amines acting as alkyl radical equivalents

Scheme 17. Demethylenative radical cyclization of 1,7-enynes enabled by P/N-heterolepitc Cu(I)-photocatalyst based on mechanism of metathesis reaction between α-amino radicals and olefin

Scheme 18. Azetidine synthesis via [3＋1] radical cascade cyclization enabled by P/N-heteroleptic Cu(I)-photocatalysts

Scheme 19. Sequential 1,n-HAT enabling construction of cyclobutoxysilanes catalyzed by P/N-heteroleptic Cu(I)-photocatalysts

Scheme 20. P/N-heteroleptic Cu(I)-photocatalyst-catalyzed radical hydroboration of alkynes and B2pin2

Scheme 21. P/N-heteroleptic Cu(I)-photocatalyst-catalyzed [3＋2] cyclization of aminocyclopropanes and functionalized alkynes

Scheme 22. Illustration of bifunctional catalytic mechanism of P/N-heteroleptic Cu(I)-photocatalyst

Scheme 23. Bifunctional Cu(I)-photosensitizer-catalyzed synthesis of pinacols from aldehydes(ketones)

Scheme 24. Photoinduced copper-catalyzed asymmetric decarboxylative alkynylation reaction between NHPI esters and terminal alkynes

Scheme 25. Synthesis of 1,2-diketones from arylynes and arylborates catalyzed by bifunctional P/N-heteroleptic Cu(I)-photocatalysts

Scheme 26. Illustration of photocatalytic reactions via dual metallic synergetic catalysis by Cu(I)-photocatalysts and other transition metals

Scheme 27. Photocatalytic cross-coupling between secondary halides and carbamates enabled by synergetic catalysis of P/N-heteroleptic Cu(I)-photocatalyst and CuBr

Scheme 28. Synthesis of 1,2-diketones from arylynes and arylborates via dual metallic synergetic catalysis by Cu(I)-photocatalyst and cobalt complex

Scheme 29. Photocatalytic reductive cyclization of alkyl chlorides via dual metallic synergetic catalysis by Cu(I)-photocatalyst and nickel complex

Scheme 30. [2＋2] photodimerization of chalcones catalyzed by P/N-heteroleptic Cu(I) photosensitizer

Scheme 31. P/N-heteroleptic Cu(I) photosensitizeer-catalyzed isomerization of (E)-olefins to (Z)-isomers

Scheme 32. P/N-heteroleptic Cu(I)-photosensitizer enabling combination of energy-transfer and photoredox catalysis for the synthesis of benzo[b]fluorenols

Scheme 33. Intermolecular crossed [2＋2] cycloaddition reaction catalyzed by a MOF-supported P/N-heteroleptic Cu(I)-photo- sensitizer

References 51

[1]	(a) Stephenson C. R. J.; Yoon T. P.; MacMillan D. W. C. Visible Light Photocatalysis in Organic Chemistry, Wiley-VCH, Weinheim, Germany, 2018. pmid: 20532341
	(b) Yoon T. P.; Ischay M. A.; Du J. Nat. Chem. 2010, 2, 527. pmid: 20532341
	(c) Narayanam J. M. R.; Stephenson C. R. J. Chem. Soc. Rev. 2011, 40, 102. doi: 10.1039/b913880n pmid: 20532341
	(d) Shaw M. H.; Twilton J.; MacMillan D. W. C. J. Org. Chem. 2016, 81, 6898. pmid: 20532341
	(e) Zou Y.-Q.; Chen J.-R.; Xiao W.-J. Angew. Chem., Int. Ed. 2013, 52, 11701. pmid: 20532341
	(f) Li K.; Long X.; Huang Y.; Zhu S. Acta Chim. Sinica 2024, 82, 658 (in Chinese). pmid: 20532341
	(李康葵, 龙先扬, 黄岳, 祝诗发, 化学学报, 2024, 82, 658.) doi: 10.6023/A24030090 pmid: 20532341
	(g) He M.; Ye Z.; Lin G.; Yin S.; Huang X.; Zhou X.; Yin Y.; Gui B.; Wang C. Acta Chim. Sinica 2023, 81, 784 (in Chinese). pmid: 20532341
	(何明慧, 叶子秋, 林桂庆, 尹晟, 黄心翊, 周旭, 尹颖, 桂波, 汪成, 化学学报, 2023, 81, 784.) doi: 10.6023/A23040178 pmid: 20532341
	(h) Lv X.; Wu Y.; Zhang B.; Guo W. Acta Chim. Sinica 2023, 81, 359 (in Chinese). pmid: 20532341
	(吕鑫, 吴仪, 张勃然, 郭炜, 化学学报, 2023, 81, 359.) doi: 10.6023/A22120487 pmid: 20532341
	(i) Yan Y.; Liang P.; Zou Y.; Yuan L.; Peng X.; Fan J.; Zhang X. Acta Chim. Sinica 2023, 81, 1642 (in Chinese). pmid: 20532341
	(闫英红, 梁平兆, 邹杨, 袁林, 彭孝军, 樊江莉, 张晓兵, 化学学报, 2023, 81, 1642.) doi: 10.6023/A23050243 pmid: 20532341
[2]	(a) Romero N. A.; Nicewicz D. A. Chem. Rev. 2016, 116, 10075.
	(b) Vega-Peñaloza A.; Mateos J.; Companyó X.; Escudero-Casao M.; DellʹAmico L. Angew. Chem., Int. Ed. 2021, 60, 1082.
	(c) Majek M.; von Wangelin A. J. Acc. Chem. Res. 2016, 49, 2316.
[3]	(a) Hockin B. M.; Li C.; Roberson N.; Zysman-Colman E. Catal. Sci. Technol. 2019, 9, 889.
	(b) Larsen C. B.; Wenger O. S. Chem.-Eur. J. 2018, 24, 2039.
[4]	(a) Reiser O. Acc. Chem. Res. 2016, 49, 1990.
	(b) Hernandez-Perez A. C.; Augusto C.; Collins S. K. Acc. Chem. Res. 2016, 49, 1557.
	(c) Hossain S.; Bhattacharyya A.; Reiser O. Science 2019, 364, eaav9713.
	(d) Beadelot J.; Oger S.; Peruško S.; Phan T.-A.; Teunens T.; Moucheron C.; Evano G. Chem. Rev. 2022, 122, 16365.
[5]	Palmer C. E. A.; McMillin D. R. Inorg. Chem. 1987, 26, 3837.
[6]	(a) Kuang S. M.; Cuttell D. G.; McMillin D. R.; Fanwick P. E.; Walton R. A. Inorg. Chem. 2002, 41, 3313.
	(b) Cuttell D. G.; Kuang S. M.; Fanwick P. E.; McMillin D. R.; Walton R. A. J. Am. Chem. Soc. 2002, 124, 6.
[7]	Augusto C.; Hernandez-Perez A. C.; Vlassova A.; Collins S. K. Org. Lett. 2012, 14, 2988. doi: 10.1021/ol300983b pmid: 22642645
[8]	(a) Luo S. P.; Mejía E.; Friedrich A.; Pazidis A.; Junge H.; Surkus A. E.; Jackstell R.; Denurra S.; Gladiali S.; Lochbrunner S.; Beller M. Angew. Chem., Int. Ed. 2013, 52, 419.
	(b) Mejía E.; Luo S. P.; Karnahl M.; Friedrich A.; Tschierlei S.; Surkus A. E.; Junge H.; Gladiali S.; Lochbrunner S.; Beller M. Chem.-Eur. J. 2013, 19, 15972.
[9]	Wang B.; Shelar D. P.; Han X. Z.; Li T. T.; Guan X.; Lu W.; Liu K.; Chen Y.; Fu W. F.; Che C. M. Chem.-Eur. J. 2015, 21, 1184. doi: 10.1002/chem.201405356 pmid: 25413572
[10]	(a) Michelet B.; Deldaele C.; Kajouj S.; Moucheron C.; Evano G. Org. Lett. 2017, 19, 3576. doi: 10.1021/acs.orglett.7b01518 pmid: 28598630
	(b) Deldaele C.; Michelet B.; Baguia H.; Kajouj S.; Romero E.; Moucheron C.; Eavano G. Chimia 2018, 72, 621. pmid: 28598630
[11]	Nitelet A.; Thevenet D.; Schiavi B.; Hardouin C.; Fournier J.; Tamion R.; Pannecoucke X.; Jubault P.; Poisson T. Chem.-Eur. J. 2019, 25, 3262.
[12]	Hunter C. J.; Boyd M. J.; May G. D.; Fimognari R. J. Org. Chem. 2020, 85, 8732.
[13]	Hernandez-Perez A. C.; Collins S. K. Angew. Chem., Int. Ed. 2013, 52, 12696.
[14]	Minozzi C.; Grenier-Petel J. C.; Parisien-Collette S.; Collins S. K. Beilstein. J. Org. Chem. 2018, 14, 2730.
[15]	Sosoe J.; Cruché C.; Morin É.; Collins S. K. Can. J. Chem. 2020, 98, 461.
[16]	Alkan-Zambada M.; Hu X. Organometallics 2018, 37, 3928.
[17]	Kern J.; Sauvage J. J. Chem. Soc., Chem. Commun. 1987, 546.
[18]	Pirtsch M.; Paria S.; Matsuno T.; Isobe H.; Reiser, O. Chem.-Eur. J. 2012, 18, 7336.
[19]	Tang X.; Dolbier W. R. Angew. Chem., Int. Ed. 2015, 54, 4246.
[20]	Wang C.; Guo M.; Qi R.; Shang Q.; Liu Q.; Wang S.; Zhao L.; Wang R.; Xu Z. Angew. Chem., Int. Ed. 2018, 57, 15841.
[21]	Wang C.; Yu Y.; Liu W. L.; Duan W. L. Org. Lett. 2019, 21, 9147.
[22]	Lyu X. L.; Huang S. S.; Song H. J.; Liu Y. X.; Wang Q. M. Org. Lett. 2019, 21, 5728.
[23]	Liu Q.; Ni Q.; Zhou Y.; Chen L.; Xiang S.; Zheng L.; Liu Y. Org. Biomol. Chem. 2023, 21, 7960.
[24]	Xiang S.; Ni Q.; Liu Q.; Zhou S.; Wang H.; Zhou Y.; Liu Y. J. Org. Chem. 2023, 88, 13248.
[25]	Xiao P.; Dumur F.; Zhang J.; Fouassier J. P.; Gigmes D.; Lalevée J. Macromolecules 2014, 47, 3837.
[26]	Mousawi A.; Kermagoret A.; Versace D.-L.; Toufaily J.; Hamieh T.; Graff B.; Dumur F.; Gigmes D.; Fouassier J. P.; Lalevée J. Polym. Chem. 2017, 8, 568.
[27]	Nicholls T. P.; Robertson J. C.; Gardiner M. G.; Bissember A. C. Chem. Commun. 2018, 54, 4589.
[28]	Bao H. Y.; Zhou B. W.; Luo S. P.; Xu Z.; Jin H. W.; Liu Y. K. ACS Catal. 2020, 10, 7563.
[29]	Zheng L. M.; Jiang Q. F.; Bao H. Y.; Zhou B. Y.; Luo S. P.; Jin H. W.; Liu Y. K. Org. Let. 2020, 22, 8888.
[30]	Peng Y.; Bao H. Y.; Zheng L. M.; Zhou Y.; Ni Q. B.; Chen X. H.; Li Y. Q.; Yan P. C.; Yang Y.-F.; Liu Y. K. Org. Lett. 2024, 26, 3218. doi: 10.1021/acs.orglett.4c00793 pmid: 38587936
[31]	Li J.; Yu L.; Peng Y.; Chen B.; Guo R.; Ma X. D.; Xue X.-S.; Liu Y. K.; Zhang G. Z. The Innovation 2022, 3, 100244.
[32]	Cao Z.; Li J.; Zhang G. Nat. Commun. 2021, 12, 6404.
[33]	Jacob C.; Baguia H.; Dubart A.; Oger S.; Thilmany P.; Beau- delot J.; Deldaele C.; Perusko S.; Landrain Y.; Michelet B.; Neale S.; Romero E.; Moucheron C.; Van Speybroeck V.; Theunissen C.; Evano G. Nat. Commun. 2022, 13, 560.
[34]	Zhong M.; Gagne Y.; Hope T. O.; Pannecoucke X.; Frenette M.; Jubault P.; Poisson T. Angew. Chem., Int. Ed. 2021, 60, 14498.
[35]	Zhong M.; Pannecoucke X.; Jubault P.; Poisson T. Chem.-Eur. J. 2021, 27, 11818.
[36]	Chen L.; Li Y.; Han M.; Peng Y.; Chen X.; Xiang S.; Gao H.; Lu T.; Luo S. P.; Zhou B.; Wu H.; Yang Y. F.; Liu Y. J. Org. Chem. 2022, 87, 15571.
[37]	(a) Hydrogen Transfer Reactions: Reductions and Beyond, Eds.: Guillena, G.; Ramón, D. J. Topics in Current Chemistry Collections, Springer International Publishing, Cham, 2016.
	(b) Gentry E. C.; Knowles R. R. Acc. Chem. Res. 2016, 49, 1546.
[38]	Sjödin M.; Irebo T.; Utas J. E. J. Am. Chem. Soc. 2006, 128, 13076.
[39]	Caron A.; Morin É.; Collins S. K. ACS Catal. 2019, 9, 9458.
[40]	Xia H. D.; Li Z. L.; Gu Q. S.; Dong X. Y.; Fang J. H.; Du X. Y.; Wang L. L.; Liu X. Y. Angew. Chem., Int. Ed. 2020, 59, 16926.
[41]	Wu D.; Cui S. S.; Bian F.; Yu W. Org. Lett. 2021, 23, 6057.
[42]	Neerathilingam N.; Prasanth K.; Anandhan R. Green Chem. 2022, 24, 8685.
[43]	(a) Twilton J.; Le C.; Zhang P.; Shaw M. H.; Evans R. W.; MacMillan D. W. C. Nat. Rev. Chem. 2017, 1, 52. pmid: 30088504
	(b) Strieth-Kalthoff F.; James M. J.; Teders M.; Pitzer L.; Glorius F. Chem. Soc. Rev. 2018, 47, 7190. doi: 10.1039/c8cs00054a pmid: 30088504
	(c) Zhou Q.-Q.; Lu L.-Q.; Xiao W.-J. Angew. Chem., Int. Ed. 2019, 58, 1586. pmid: 30088504
	(d) Strieth-Kalthoff F.; Glorius F. Chem 2020, 6, 1888. pmid: 30088504
[44]	Ahn J. M.; Peters J. C.; Fu G. C. J. Am. Chem. Soc. 2017, 139, 18101.
[45]	Call A.; Casadevall C.; Acuna-Pares F.; Casitas A.; Lloret-Fillol J. Chem. Sci. 2017, 8, 4739.
[46]	Claros M.; Ungeheuer F.; Franco F.; Martin-Diaconescu V.; Casitas A.; Lloret-Fillol J. Angew. Chem., Int. Ed. 2019, 58, 4869.
[47]	Welin E. R.; Le C.; Arias-Rotondo D. M.; McCusker J. K.; MacMillan D. W. C. Science 2017, 355, 380. doi: 10.1126/science.aal2490 pmid: 28126814
[48]	Wu Q.-A.; Ren C.-C.; Chen F.; Wang T.-Q.; Zhang Y.; Liu X.-F.; Chen J.-B.; Luo S.-P. Tetrahedron Lett. 2021, 72, 153091.
[49]	Cruché C.; Neiderer W.; Collins S. K. ACS Catal. 2021, 11, 8829.
[50]	Zheng L.; Xue H.; Zhou B.; Luo S. P.; Jin H.; Liu Y. Org Lett. 2021, 23, 4478.
[51]	Guo J.; Xia Q.; Tang W. Y.; Li Z.; Wu X.; Liu L.-J.; To W.-P.; Shu H.-X.; Low K.-H.; Chow P. C. Y.; Lo T. W. B.; He J. Nat. Catal. 2024, 7, 307.

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