光催化的由亚胺合成胺研究进展

doi:10.6023/cjoc202509025

摘要/Abstract

在过去的十余年间,有机光化学作为有机化学的前沿领域,受到了广泛关注。相较于传统方法,光催化反应具有条件温和、官能团耐受性高等优点,且常有独特的反应性。作为光催化的重要领域,亚胺化合物的转化也不断取得新的进展。光催化下,亚胺可以被单电子还原为α-氨基烷基自由基,其反应活性得到了重塑,甚至可以极性反转作为亲核试剂参与反应。在天然产物及药物分子的结构中,氨基及氮杂环是十分常见且重要的结构。因此,通过光催化条件实现亚胺化合物向胺类化合物的转化,无疑拓展了传统的合成模式,为药物化学及合成化学等领域提供了崭新的研究方法。本文以反应活性、官能团耐受性等方面为重点,总结了由亚胺化合物通过光催化反应生成α-氨基烷基自由基合成胺类化合物的发展和研究现状。

关键词: 光催化, 亚胺, 胺, 自由基

Over the past decade, photocatalysis has emerged as one of the frontiers in organic chemistry, attracted tremendous interest from the synthetic community. Compared to traditional methods, photocatalytic reactions offer advantages such as mild conditions, high functional group tolerance and unique reactivity and selectivity. As an important area of photocatalysis, the transformation of imines is undergoing continuous advancements. Under photocatalytic conditions, the reactivity of imines is reshaped, allowing them to undergo single-electron reduction to form α-aminoalkyl radicals—a process that can even reverse their polarity, enabling them to act as carbon nucleophiles. N-heterocycles and amines are among the most prevalent and important organic compounds, which are found in numerous alkaloids and pharmaceutical molecules. Therefore, the conversion of imine compounds to amines under photocatalytic conditions have introduced new methodologies to solve important problems in the synthesis of drugs and beyond, which were hardly achieved by traditional synthetic strategies. This review summarized the research progress on the photocatalytic synthesis of amines from imines via α-aminoalkyl radicals, with a focus on selectivity and functional group tolerance.

Key words: photocatalysis, imine, amine, radical

引用此文

赵子鸣, 郑剑峰, 黄培强. 光催化的由亚胺合成胺研究进展[J]. 有机化学, doi: 10.6023/cjoc202509025.

Zhao, Ziming, Zheng, Jianfeng, Huang, Peiqiang. Progress on the Photocatalytic Synthesis of Amines from Imines[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202509025.

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参考文献

[1] (a) Huang J.; Huang Y.; Hu, P.Chin.J.Org.Chem.2025, 45, 1509.
(b) Murray, P.R.D.; Cox, J.H.; Chiappini, N.D.; Roos, C.B.; McLoughlin, E.A.; Hejna, B.G.; Nguyen, S.T.; Ripberger, H.H.; Ganley, J.M.; Tsui, E.; Shin, N.Y.; Koronkiewicz, B.; Qiu, G.; Knowles, R.R.Chem.Rev. 2022, 122, 2017.
(c) Cannalire R.; Pelliccia S.; Sancineto L.; Novellino E.; Tron G.C.; Giustiniano, M.Chem.Soc.Rev.2021, 50, 766.
(d) Romero N.A.; Nicewicz, D.A.Chem.Rev.2016, 116, 10075.
(e) Xuan J.; Xiao, W.J.Angew.Chem., Int.Ed.2012, 51, 6828.
(f) Narayanam J.M.R.; Stephenson, C.R.J.Chem.Soc.Rev.2011, 40, 102.
[2] (a) Wang H.; Xu T.Chem.Catal.2024, 4, 100952.
(b) Talekar S.S.; Dutta S.; Mane M.V.; Maity, B.Eur.J.Org.Chem.2024, 27, e202301312.
(c) Li, W.; Wang, Y.; Chen, J.; Shi, D.; Zhang, L.; Yu, X.; Wang, Z.-[J].Chin.J.Org.Chem.2024, 44, 2110.
(d) Li, W.; Sun, B.; Zhang, L.; Mo, F.Chin.J.Org.Chem.2024, 44, 2961.
(e) Yuan, P.; Zhu, C.; Meng, Q.Chin.J.Org.Chem.2024, 44, 2997.
(f) Hou, Y.; Cheng, Y.; Chen, B.; Tung, C.; Wu, L.Chin.J.Org.Chem.2023, 43, 1012.
(g) Liu, J.; Peng, J.; Bai, Y.; Li, J.; Song, Z.; Liu, P.; Ouyang, T.; Lan, H.Chin.J.Org.Chem.2023, 43, 3558.
(h) Bellotti, P.; Huang, H.M.; Faber, T.; Glorius, F.Chem.Rev.2023, 123, 4237.
(i) Cullen S.T.J.; Friestad G.K.Synthesis2021, 53, 2319.
(j) Yu, S.; Zhang, H.H.; Zhao, J.J.Synthesis 2021, 53, 1706.
(k) Garrido-Castro A.F.; Maestro M.C.; Alemán J.Catalysts2020, 10, 562.
(l) Huang, T.; Du, P.; Lin, Y.M.Chin.J.Chem.2025, 43, 2566.
[3] (a) Nicewicz D.A.; MacMillan, D.W.C.Science2008, 322, 77.
(b) Wang T.-C.; Mai B.K.; Zhang Z.; Bo Z.; Li J.; Liu P.; Yang Y.Nature2024, 629, 98.
(c) Liu X.; Sau A.; Green A.R.; Popescu M.V.; Pompetti N.F.; Li Y.; Zhao Y.; Paton R.S.; Damrauer N.H.; Miyake G.M.Nature2025, 637, 601.
[4] (a) Doeun D.; Davaatseren M.; Chung, M.S.Food Sci.Biotechnol.2017, 26, 1463.
(b) Froidevaux V.; Negrell C.; Caillol S.; Pascault J.P.; Boutevin B.Chem.Rev.2016, 116, 14181.
(c) Dhyani, P.; Quispe, C.; Sharma, E.; Bahukhandi, A.; Sati, P.; Attri, D.C.; Szopa, A.; Sharifi-Rad, J.; Docea, A.O.; Mardare, I.; Calina, D.; Cho, W.C.Cancer Cell Int.2022, 22, 206.
[5] (a) Fang J.; Tian R.; Chen J.; Liu, X.Chin.J.Org.Chem.2025, 45, 22.
(b) Cabré, A.; Verdaguer, X.; Riera, A.Chem.Rev.2022, 122, 269.
(c) Trowbridge A.; Walton S.M.; Gaunt, M.J.Chem.Rev.2020, 120, 2613.
[6] (a) Reshi, N.U.D.; Saptal, V.B.; Beller, M.; Bera, J.K.ACS Catal.2021, 11, 13809.
(b) Egorov I.N.; Santra S.; Kopchuk D.S.; Kovalev I.S.; Zyryanov G.V.; Majee A.; Ranu B.C.; Rusinov V.L.; Chupakhin, O.N.Adv.Synth.Catal.2020, 362, 4293.
(c) Morisaki, K.; Morimoto, H.; Ohshima, T.ACS Catal.2020, 10, 6924.
[7] (a) Wan, L.-Q.; Cao, J.-G.; Niu, D.; Zhang, X.Org.Lett.2021, 23, 3818.
(b) Zhao B.; Chen W.W.Synlett2020, 31, 1543.
[8] (a) Bloch, R.Chem.Rev. 1998, 98, 1407.
(b) Dhayalan, V.; Sharma, D.; Chatterjee, R.; Dandela, R.Eur.J.Org.Chem.2023, 26, e202300285.
[9] (a) Nakajima, K.; Miyake, Y.; Nishibayashi, Y. Acc.Chem.Res. 2016, 49, 1946.
(b) Su Y.-L.; Doyle M.P.Synthesis2022, 54, 545.
[10] Lee K.N.; Lei Z.; Ngai M.-Y.J.Am.Chem.Soc.2017, 139, 5003.
[11] Rossolini T.; Leitch J.A.; Grainger R.; Dixon D.J.Org.Lett.2018, 20, 6794.
[12] Cao K.; Tan S.M.; Lee R.; Yang S.; Jia H.; Zhao X.; Qiao B.; Jiang Z.J.Am.Chem.Soc.2019, 141, 5437.
[13] Lefebvre Q.; Porta R.; Millet A.; Jia J.; Rueping M.Chem.Eur.J.2020, 26, 1363.
[14] Kammer L.M.; Krumb M.; Spitzbarth B.; Lipp B.; Kuhlborn J.; Busold J.; Mulina O.M.; Terentev A.O.; Opatz T.Org.Lett.2020, 22, 3318.
[15] Chen Y.; Yan H.; Liao Q.; Zhang D.; Lin S.; Hao E.; Murtaza R.; Li C.; Wu C.; Duan C.; Shi L.Angew.Chem., Int.Ed.2022, 61, e202204516.
[16] Ghosh S.K.; He L.; Tang Z.; Comito, R.J. J.Org.Chem.,2023, 88, 15209.
[17] Harris G.R.; Trowbridge A.D.; Gaunt, M.J.Org.Lett.2023, 25, 861.
[18] (a) Ramadhar T.R.; Batey R.A.Synthesis2011, 2011, 1321.
(b) Kondratyev N.S.; Malkov, A.V.Beilstein J.Org.Chem.2024, 20, 2349.
[19] Qi L.; Chen, Y.Angew.Chem., Int.Ed.2016, 55, 13312.
[20] Huang L.Q.; Yang D.Y.; Dong C.L.; He Y.H.; Guan, Z., Adv.Synth.Catal.2023, 365, 2553.
[21] (a) Mukherjee S.; Yang J.W.; Hoffmann S.; List B.Chem.Rev.2007, 107, 5471.
(b) Allen, A.E.; MacMillan, D.W.C.Chem.Sci.2012, 3, 633.
[22] (a) Fu Z.; Xu J.; Zhu T.; Leong W.W.Y.; Chi, Y.R.Nat.Chem.2013, 5, 835.
(b) Mo J.; Shen L.; Chi, Y.R.Angew.Chem., Int.Ed.2013, 52, 8588.
(c) Huang Z.; Dong, G.J.Am.Chem.Soc.2013, 135, 17747.
[23] Jeffrey J.L.; Petronijevic F.R.; MacMillan, D.W.C.J.Am.Chem.Soc.2015, 137, 8404.
[24] Dolcini L.; Gandini T.; Castiglioni R.; Bossi A.; Penconi M.; Dal Corso A.; Gennari C.; Pignataro, L.J.Org.Chem.2023, 88, 14283.
[25] Wang R.; Ma M.; Gong X.; Fan X.; Walsh, P.J.Org.Lett.2019, 21, 27.
[26] Zhang H.-H.; Yu, S.J.Org.Chem.2017, 82, 9995.
[27] Cardinale L.; Schmotz M.W.S.; Konev, M.O.; Jacobi von Wangelin, A.Org.Lett.2022, 24, 506.
[28] Song X.; Zhang Y.; Li Y.; Zhao X.; Yin Y.; Ban X.; Jiang Z.ACS Catal.2023, 13, 6396.
[29] Zhong Z.; Wu H.; Chen X.; Luo Y.; Yang L.; Feng X.; Liu, X.J.Am.Chem.Soc.2024, 146, 20401.
[30] Chen M.; Zhao X.; Yang C.; Xia W.Org.Lett.2017, 19, 3807.
[31] Fan X.; Gong X.; Ma M.; Wang R.; Walsh, P.J.Nat.Commun.2018, 9, 4936.
[32] Zhang H.-H.; Yu S.Org.Lett.2019, 21, 3711.
[33] Fava E.; Millet A.; Nakajima M.; Loescher S.; Rueping M.Angew.Chem., Int.Ed.2016, 55, 6776.
[34] Xia Q.; Tian H.; Dong J.; Qu Y.; Li L.; Song H.; Liu Y.; Wang Q.Chem.Eur.J.2018, 24, 9269.
[35] Nicastri M.C.; Lehnherr D.; Lam Y.-h.; DiRocco D.A.; Rovis, T.J.Am.Chem.Soc.2020, 142, 987.
[36] Zhou N.; Yuan X.A.; Zhao Y.; Xie J.; Zhu C.Angew.Chem., Int.Ed.2018, 57, 3990.
[37] Vazquez-Amaya L.Y.; Dootselaere B.; Ojeda-Carralero G.M.; Pillitteri S.; Van der Eycken J.; Van der Eycken, E.V.; Sharma, U.K.Org.Lett.2023, 25, 4010.
[38] Leitch J.A.; Fuentes de Arriba, A.L.; Tan J.; Hoff O.; Martinez C.M.; Dixon, D.J.Chem.Sci.2018, 9, 6653.
[39] Leitch J.A.; Rogova T.; Duarte F.; Dixon D.J.Angew.Chem., Int.Ed.2020, 59, 4121.
[40] (a) Saibabu Kotti, S.R.; Timmons, C.; Li, G. Chem.Biol.Drug Des.2006, 67, 101.
(b) Foubelo, F.; Nájera, C.; Retamosa, M.G.; Sansano, J.M.; Yus, M.Chem.Soc.Rev.2024, 53, 7983.
[41] Nakajima M.; Fava E.; Loescher S.; Jiang Z.; Rueping, M.Angew.Chem., Int.Ed.2015, 54, 8828.
[42] Okamoto S.; Ariki R.; Tsujioka H.; Sudo, A.J.Org.Chem.2017, 82, 9731.
[43] Gualandi A.; Rodeghiero G.; Della Rocca, E.; Bertoni, F.; Marchini, M.; Perciaccante, R.; Jansen, T.P.; Ceroni, P.; Cozzi, P.G.Chem.Commun.2018, 54, 10044.
[44] Rong J.; Seeberger P.H.; Gilmore K.Org.Lett.2018, 20, 4081.
[45] van As D.J.; Connell T.U.; Brzozowski M.; Scully A.D.; Polyzos A.Org.Lett.2018, 20, 905.
[46] Guo X.; Wenger, O.S.Angew.Chem., Int.Ed.2018, 57, 2469.
[47] Wang R.; Ma M.; Gong X.; Panetti G.B.; Fan X.; Walsh, P.J.Org.Lett.2018, 20, 2433.
[48] (a) Wu H.L.; Qi M.Y.; Tang Z.R.; Xu, Y.J.J.Mater.Chem.A2023, 11, 3262.
(b) Weiss, E.A.ACS Energy Lett.2017, 2, 1005.
[49] Xi Z.W.; Yang L.; Wang D.Y.; Pu C.D.; Shen Y.M.; Wu C.D.; Peng, X.G.J.Org.Chem.2018, 83, 11886.