Fundamentals of electron upconversion and its applications in organocatalysis

doi:10.6023/cjoc202506036

Abstract

Photon upconversion, an anti-Stokes process that elevates photon energy, has become indispensable in photonic materials and optoelectronic devices. Inspired by this physical phenomenon, chemists have recently transposed its fundamental concept to organic catalysis, establishing electron upconversion as an innovative catalytic paradigm. The thermodynamic and kinetic advantages of electron upconversion originate from two key features: (1) radical transformations exhibit significantly reduced energy release and accelerated reaction rates compared to ground-state processes; (2) the upconverted intermediates complete catalytic cycles via facile electron transfer mechanisms. Three principal electron upconversion strategies have been developed: molecular dissociation (e.g., homolytic bond cleavage), molecular association (e.g., three-electron bond formation), and super-electron-donor systems. These groundbreaking approaches have demonstrated remarkable efficacy in pivotal organic transformations including C-N cross-coupling and Si-Si bond activation, opening new avenues for sustainable catalysis development. This article provides a comprehensive discussion of the theoretical mechanisms (including thermodynamic and kinetic fundamentals), reaction types, and applications in catalytic synthesis, while also summarizing cutting-edge developments in related fields.

Key words: electron upconversion, dissociation, association, super-electron-donors, reductants

Cite this article

Zhu Wenhui, Yang Jin-Dong. Fundamentals of electron upconversion and its applications in organocatalysis[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202506036.

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References

[1] (a) Dong, H.; Sun, L.-D.; Yan, C.-H. Chem. Soc. Rev. 2015, 44, 1608–1634.
(b) Nadort, A.; Zhao, J.; Goldys, E. M. Nanoscale 2016, 8, 13099–13130.
(c) Zhou, B.; Yan, L.; Huang, J.; Liu, X.; Tao, L.; Zhang, Q. Nat. Photonics 2020, 14, 760–766.
(d) Liang, W.; Nie, C.; Du, J.; Han, Y.; Zhao, G.; Yang, F.; Liang, G.; Wu, K. Nat. Photon. 2023, 17, 346–353.
[2] Richards, B. S.; Hudry, D.; Busko, D.; Turshatov, A.; Howard, I. A. Chem. Rev. 2021, 121, 9165–9195.
[3] (a) Schulze, T. F.; Schmidt, T. W. Energy Environ. Sci. 2014, 8, 103–125.
(b) Bharmoria, P.; Bildirir, H.; Moth-Poulsen, K. Chem. Soc. Rev. 2020, 49, 6529–6554.
(c) Gao, C.; Wong, W. W. H.; Qin, Z.; Lo, S.; Namdas, E. B.; Dong, H.; Hu, W. Adv. Mater. 2021, 33, 2100704.
(d) Yao, B.; Sun, H.; He, Y.; Wang, S.; Liu, X. Int. J. Mol. Sci. 2022, 23, 8041.
(e) Huang, L.; Han, G. Nat. Rev. Chem. 2024, 8, 238–255.
[4] (a) Hou, H.; Cheng, Y.; Chen, B.; Tong, Z.; Wu, L. Chin. J. Org. Chem. 2023, 43, 1012–1022 (in Chinese)
(侯虹宇, 程元元, 陈彬, 佟振合, 吴骊珠, 有机化学, 2023, 43, 1012–1022).
(b) Chen, Y.; He, J.; Zhang, B.; Wang, Y.; Kong, L.; Qian, W.; Wang, N.; Duan, W.; Ouyang, Y.; Zhu, C.; Xu, H. Chin. J. Org. Chem. 2024, 44, 748–779 (in Chinese)
(陈远航, 何劲宇, 张博, 王延钊, 孔令轩, 钱伟烽, 王娜娜, 段闻喜, 欧阳妍妍, 朱翠菊, 徐浩, 有机化学, 2024, 44, 748–779).
(c) Ye, Z.; Liu, H.; Zhang, F. Chin. J. Org. Chem. 2024, 44, 840–870 (in Chinese)
(叶增辉, 刘华清, 张逢质, 有机化学, 2024, 44, 840–870).
(d) Gao, C.; Liu, X.; Wang, M.; Liu, S.; Zhu, T.; Zhang, Y.; Hao, E.; Yang, Q. Chin. J. Org. Chem. 2024, 44, 673–727 (in Chinese)
(高淳, 刘欣, 王明慧, 刘淑贤, 朱婷婷, 张怡康, 郝二军, 杨启亮, 有机化学, 2024, 44, 673–727).
[5] Alabugin, I. V.; Eckhardt, P.; Christopher, K. M.; Opatz, T. J. Am. Chem. Soc. 2024, 146, 27233–27254.
[6] (a) Studer, A.; Curran, D. P. Nat. Chem. 2014, 6, 765–773.
(b) Francke, R.; Little, R. D. ChemElectroChem 2019, 6, 4373–4382.
[7] (a) Mabon, G.; Le Guillanton, G.; Simonet, J. J. Electroanal. Chem. Interfacial Electrochem. 1981, 130, 387–390.
(b) Park, Y. S.; Little, R. D. J. Org. Chem. 2008, 73, 6807–6815.
(c) Pedersen, S. K.; Ulfkjær, A.; Newman, M. N.; Yogarasa, S.; Petersen, A. U.; Sølling, T. I.; Pittelkow, M. J. Org. Chem. 2018, 83, 12000–12006.
(d) Broese, T.; Roesel, A. F.; Prudlik, A.; Francke, R. Org. Lett. 2018, 20, 7483–7487.
[8] (a) Okada, Y.; Yamaguchi, Y.; Ozaki, A.; Chiba, K. Chem. Sci. 2016, 7, 6387–6393.
(b) Imada, Y.; Okada, Y.; Chiba, K. Beilstein J. Org. Chem. 2018, 14, 642–647.
[9] Amatore, C.; Pinson, J.; Saveant, J. M.; Thiebault, A. J. Am. Chem. Soc. 1982, 104, 817–826.
[10] Syroeshkin, M. A.; Kuriakose, F.; Saverina, E. A.; Timofeeva, V. A.; Egorov, M. P.; Alabugin, I. V. Angew. Chem. Int. Ed. 2019, 58, 5532–5550.
[11] Wu, Y.; Yan, Y.; Liao, W. Chin. J. Org. Chem. 2023, 43, 3713–3727 (in Chinese)
(吴宇恒, 颜岩, 寮渭巍, 有机化学, 2023, 43, 3713–3727).
[12] Syroeshkin, M. A.; Krylov, I. B.; Hughes, A. M.; Alabugin, I. V.; Nasybullina, D. V.; Sharipov, M. Yu.; Gultyai, V. P.; Terent’ev, A. O. J. Phys. Org. Chem. 2017, 30, e3744.
[13] Alvarez, E. M.; Karl, T.; Berger, F.; Torkowski, L.; Ritter, T. Angew. Chem. Int. Ed. 2021, 60, 13609–13613.
[14] Dell’Erba, C.; Houmam, A.; Novi, M.; Petrillo, G.; Pinson, J. J. Org. Chem. 1993, 58, 2670–2677.
[15] Vacher, M.; Fdez. Galván, I.; Ding, B.-W.; Schramm, S.; Berraud-Pache, R.; Naumov, P.; Ferré, N.; Liu, Y.-J.; Navizet, I.; Roca-Sanjuán, D.; Baader, W. J.; Lindh, R. Chem. Rev. 2018, 118, 6927–6974.
[16] Stringle, D. L. B.; Magri, D. C.; Workentin, M. S. Chem. –Eur. J. 2010, 16, 178–188.
[17] Lübbesmeyer, M.; Mackay, E. G.; Raycroft, M. A. R.; Elfert, J.; Pratt, D. A.; Studer, A. J. Am. Chem. Soc. 2020, 142, 2609–2616.
[18] Owatari, Y.; Iseki, S.; Ogata, D.; Yuasa, J. Chem. Sci. 2022, 13, 5261–5267.
[19] Burykina, J. V.; Shlapakov, N. S.; Gordeev, E. G.; König, B.; Ananikov, V. P. Chem. Sci. 2020, 11, 10061–10070.
[20] Greener, A. J.; Ubysz, P.; Owens-Ward, W.; Smith, G.; Ocaña, I.; Whitwood, A. C.; Chechik, V.; James, M. J. Chem. Sci. 2021, 12, 14641–14646.
[21] (a) Lampard, C.; Murphy, J. A.; Lewis, N. J. Chem. Soc., Chem. Commun. 1993, 295–297.
(b) Burkholder, C.; Dolbier, W. R.; Médebielle, M. J. Org. Chem. 1998, 63, 5385–5394.
[22] (a) Murphy, J. A.; Khan, T. A.; Zhou, S.; Thomson, D. W.; Mahesh, M. Angew. Chem. Int. Ed. 2005, 44, 1356–1360.
(b) Murphy, J. A.; Zhou, S.; Thomson, D. W.; Schoenebeck, F.; Mahesh, M.; Park, S. R.; Tuttle, T.; Berlouis, L. E. A. Angew. Chem. Int. Ed. 2007, 119, 5270–5275.
(c) Doni, E.; Murphy, J. A. Chem. Commun. 2014, 50, 6073–6087.
(d) Broggi, J.; Terme, T.; Vanelle, P. Angew. Chem. Int. Ed. 2014, 126, 392–423.
(e) Hanson, S. S.; Doni, E.; Traboulsee, K. T.; Coulthard, G.; Murphy, J. A.; Dyker, C. A. Angew. Chem. Int. Ed. 2015, 127, 11388–11391.
[23] Rohrbach, S.; Shah, R. S.; Tuttle, T.; Murphy, J. A. Angew. Chem. Int. Ed. 2019, 58, 11454–11458.
[24] Assani, N.; Delfau, L.; Smits, P.; Redon, S.; Kabri, Y.; Tomás-Mendivil, E.; Vanelle, P.; Martin, D.; Broggi, J. Chem. Sci. 2024, 15, 14699–14704.
[25] Zhang, L.; Jiao, L. Chem. Sci. 2018, 9, 2711–2722.
[26] Bai, L.; Jiao, L. Chem 2023, 9, 3245–3267.
[27] (a) Sandfort, F.; Strieth‐Kalthoff, F.; Klauck, F. J. R.; James, M. J.; Glorius, F. Chem. –Eur. J. 2018, 24, 17210–17214.
(b) Inial, A.; Morlet-Savary, F.; Lalevée, J.; Gaumont, A.; Lakhdar, S. Org. Lett. 2020, 22, 4404–4407.
[28] (a) Wu, Z.; Li, S.; Xu, H. Angew. Chem. Int. Ed. 2018, 57, 14070–14074.
(b) Wu, Z.; Li, S.; Xu, H. Angew. Chem. Int. Ed. 2018, 130, 14266–14270.
[29] Eckhardt, P.; Elliot, Q.; Alabugin, I. V.; Opatz, T. Chem. –Eur. J. 2022, 28, e202201637.
[30] (a) Evoniuk, C. J.; Gomes, G. D. P.; Hill, S. P.; Fujita, S.; Hanson, K.; Alabugin, I. V. J. Am. Chem. Soc. 2017, 139, 16210–16221.
(b) Elliott, Q.; Dos Passos Gomes, G.; Evoniuk, C. J.; Alabugin, I. V. Chem. Sci. 2020, 11, 6539–6555.
[31] Balycheva, V. A.; Chabuka, B. K.; Kuhn, L. R.; Shangin, P. G.; Akyeva, A. Ya.; Krylova, I. V.; Korolev, V. A.; Lalov, A. V.; Egorov, M. P.; Alabugin, I. V.; Syroeshkin, M. A. J. Phys. Chem. C 2024, 128, 4581–4599.
[32] (a) Budén, M. E.; Guastavino, J. F.; Rossi, R. A. Org. Lett. 2013, 15, 1174–1177.
(b) Dewanji, A.; Murarka, S.; Curran, D. P.; Studer, A. Org. Lett. 2013, 15, 6102–6105.
(c) Wertz, S.; Leifert, D.; Studer, A. Org. Lett. 2013, 15, 928–931.
(d) Leifert, D.; Studer, A. Org. Lett. 2015, 17, 386–389.
(e) Hartmann, M.; Daniliuc, C. G.; Studer, A. Chem. Commun. 2015, 51, 3121–3123.
(f) Xu T.; Qi X.; Lan Y. Sci. Sin. Chim. 2016, 46, 616–622 (in Chinese)
(徐婷, 戚孝天, 蓝宇, 中国科学: 化学, 2016, 46, 616–622).
[33] Yanagisawa, S.; Ueda, K.; Taniguchi, T.; Itami, K. Org. Lett. 2008, 10, 4673–4676.
[34] Smith, A. J.; Poole, D. L.; Murphy, J. A. Sci. China Chem. 2019, 62, 1425–1438.
[35] Capaldo, L.; Ravelli, D. Chem. Commun. 2019, 55, 3029–3032.
[36] (a) Hou J.; Huang Y.; Li H.; Wan Y.; Shao Y.; Zhan L.; Wang D.; Li B. Chin. J. Org. Chem. 2024, 44, 3117–3135 (in Chinese)
(侯静, 黄燕, 李浩, 万远翠, 邵雨, 詹乐武, 王定海, 李斌栋, 有机化学, 2024, 44, 3117–3135).
(b) Xu, H.; Jiang, H.; Kan, L.; Xu, P.; Zhu, X. Chin. J. Org. Chem. 2024, 44, 3241–3248 (in Chinese)
(徐辉, 蒋慧娴, 阚磊, 徐佩, 朱旭, 有机化学, 2024, 44, 3241–3248).
[37] Hendy, C. M.; Smith, G. C.; Xu, Z.; Lian, T.; Jui, N. T. J. Am. Chem. Soc. 2021, 143, 8987–8992.
[38] (a) Paulisch, T. O.; Strieth-Kalthoff, F.; Henkel, C.; Pitzer, L.; Guldi, D. M.; Glorius, F. Chem. Sci. 2020, 11, 731–736.
(b) Chabuka, B. K.; Alabugin, I. V. J. Am. Chem. Soc. 2023, 145, 19354–19367.
[39] (a) Zhang, J.; Yang, J.; Cheng, J. Angew. Chem. Int. Ed. 2019, 58, 5983–5987.
(b) Zhang, J.; Yang, J.-D.; Cheng, J.-P. Chem. Sci. 2020, 11, 3672–3679.
(c) Zhang, J.; Yang, J.-D.; Cheng, J.-P. Chem. Sci. 2020, 11, 8476–8481.
(d) Zhang, J.; Zhao, X.; Yang, J.-D.; Cheng, J.-P. J. Org. Chem. 2022, 87, 294–300.

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