Recent Progress in C—H Functionalization of N-Sulfonyl Ketimines

doi:10.6023/cjoc202512014

Abstract

N-Sulfonyl ketimines have attracted great attention due to unique structure, significant biological activities and potential medicinal value. As versatile synthetic building blocks, N-sulfonyl ketimines have wide applications in synthetic chemistry, for the construction of complex and chiral heterocycles. In this review, recent advances in N-sulfonylketimide functionalization over the past five years are summarized. Based on the different reaction types involved, representative examples and detailed reaction mechanisms are categorized and discussed in detail.

Key words: N-sulfonyl ketimine, alkylation, annulation, amination, acylation

Cite this article

Jinfeng Shang, Hongtao Ji, Jiayao Huang, Rongqiang Li. Recent Progress in C—H Functionalization of N-Sulfonyl Ketimines[J]. Chinese Journal of Organic Chemistry, 2026, 46(6): 2275-2309.

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Fig. & Tab. 29

Figure 1. Representative biologically active N-sulfonyl keti- mines moieties

Scheme 1. Synthesis of N-sulfonyl ketimines

Figure 2. C—H functionalization of N-sulfonyl ketimines

Scheme 2. Silver-catalyzed decarboxylative C—H functionalization of N-sulfonyl ketimines with aliphatic carboxylic acids

Scheme 3. Ag-catalyzed ring-opening for C—H functionalization of N-sulfonyl ketimines with tertiary cycloalkanols

Scheme 4. Solvent-controlled silver catalyzed radical transformation of α-imino-oxy acids with N-sulfonyl ketimines

Scheme 5. Silver-catalyzed oxidative ring-opening of cyclic aliphatic amines for C—H alkylation of N-sulfonyl ketimines

Scheme 6. Photoinduced decatungstate-catalyzed direct coupling of cycloalkanes and N-sulfonyl ketimines

Scheme 7. External photocatalyst-free C—H alkylation of N- sulfonyl ketimines with alkanes

Scheme 8. Nd@C3N4-photoredox/chlorine dual catalyzed alkylation

Scheme 9. CeCl3-catalyzed C—H alkylation of N-sulfonyl ketimines with alkanes and ether via photoinduced LMCT chlorine-radical and air

Scheme 10. Catalyst-free, air-mediated C(sp2)—H alkylation of N-sulfonyl ketimines with alkylboronic acids

Scheme 11. Photoinduced metal- and photosensitizer-free decarbonylative C—H alkylation

Scheme 12. Iron catalyzed alkylation of N-sulfonyl ketimines with olefins via metal hydride atom transfer

Scheme 13. Perovskite catalyzed annulation reaction of N-sulfonyl ketimines

Scheme 14. Oxygen-doped carbon nitride catalyzed decarboxylative annulation reactions

Scheme 15. Ferrocene-mediated photocatalytic annulation of N-sulfonyl ketimines on polycrystalline WSe2

Scheme 16. H-bond promoted NPh3-mediated SrTiO3-photocatalyzed cascade decarboxylative coupling/annulation of benzo[d]isothiazole 1,1-dioxides

Scheme 17. Eosin Y catalyzed homogeneous cyclization of cyclic N-sulfonyl ketimines

Scheme 18. EtOH-catalyzed electrosynthesis of imidazolidine-fused sulfamidates

Scheme 19. Supporting-electrolyte-free electrochemical [2+2+1] annulation of five-membered N-sulfonyl ketimines

Scheme 20. Electro-catalyzed, solvent-controlled divergent decarboxylative annulation and hydroaminomethylation of N-sulfonyl ketimines

Scheme 21. Organocatalytic asymmetric [3+2]-annulations of γ-sulfonamido/γ-hydroxy-α,β-unsaturated ketones with N-sulfonyl ketimines: synthesis of chiral polyheterotricyclic imidazolidines and oxazolidines

Scheme 22. An eosin Y-catalyzed C(sp2)—N cross coupling reaction of N-sulfonyl ketimines with cyclic aliphatic amines

Scheme 23. Electrochemically driven oxidative C—H/N—H cross-coupling reactions of N-sulfonyl ketimines with primary anilines and secondar amines

Scheme 24. Potassium-modified carbon nitride photocatalyzed-aminoacylation of N-sulfonyl ketimines

Scheme 25. Catalyst-free direct ring-opening of N-sulfonyl ketimines with aliphatic primary amines to construct o-hydroxy schiff bases

Scheme 26. Cu(OAc)2/DABCO-mediated domino reaction of N-sulfonyl ketimines with vinyl malononitriles to access 6-hydroxyaryl- 2-aminonicotinonitriles

Scheme 27. Assembly of nitrated isoxazoles using benzoxathiazine-2,2-dioxides as C1 synthons

References 46

[1]	(a) Zhu, Z.-Q.; Ye, L.-H.; Wu, Y.; Guo, Z.-Q.; Shi, F. Acta Chim. Sinica 2025, 83, 1465. (in Chinese) doi: 10.6023/A25070265
	(朱子琦, 叶乐华, 吴怡, 郭梓圻, 石枫, 化学学报, 2025, 83, 1465.)
	(b) Tang, J.-H.; Zhou, C.-Y.; Wang, C.-M. Acta Chim. Sinica 2025, 83, 557. (in Chinese)
	(唐俊鸿, 周聪颖, 王成明, 化学学报, 2025, 83, 557.)
	(c) Bower, J. F.; Rujirawanich, J.; Gallagher, T. Org. Biomol. Chem. 2010, 8, 1505.
[2]	(a) Zimmermann, S.; Akbarzadeh, M.; Otte, F.; Strohmann, C.; Sankar, M. G.; Ziegler, S.; Pahl, A.; Sievers, S.; Kumar, K. Chemistry 2019, 25, 15498.
	(b) Chen, X.; Zhu, C.; Guo, F.; Qiu, X.; Yang, Y.; Zhang, S.; He, M.; Parveen, S.; Jing, C.; Li, Y.; Ma, B. J. Med. Chem. 2010, 53, 8330.
[3]	Zhao, Q. Q.; Hu, X. Q. Molecules 2020, 25.
[4]	Cannalire, R.; Tarantino, D.; Astolfi, A.; Barreca, M. L.; Sabatini, S.; Massari, S.; Tabarrini, O.; Milani, M.; Querat, G.; Mastrangelo, E.; Manfroni, G.; Cecchetti, V. Eur. J. Med. Chem. 2018, 143, 1667.
[5]	Shang, E.; Wu, Y.; Liu, P.; Liu, Y.; Zhu, W.; Deng, X.; He, C.; He, S.; Li, C.; Lai, L. Bioorg. Med. Chem. Lett. 2014, 24, 2764.
[6]	Guin, S.; Majee, D.; Samanta, S. Chem. Commun. 2021, 57, 9010.
[7]	(a) Park, J. U.; Hyun Kim, J. Adv. Synth. Catal. 2024, 366, 3926.
	(b) Ahn, H.-I.; Park, J.-U.; Xuan, Z.; Kim, J. H. Org. Biomol. Chem. 2020, 18, 9826.
[8]	Wright, J. B. J. Org. Chem. 1965, 30, 3960.
[9]	(a) Liu, Q. P.; Chen, L. M.; Zhou, C.; Guo, X. Q.; Kang, T. R. Asian J. Org. Chem. 2023, 12, 1.
	(b) Xia, A.-J.; Kang, T.-R.; He, L.; Chen, L.-M.; Li, W.-T.; Yang, J.-L.; Liu, Q.-Z. Angew. Chem., Int. Ed. 2016, 55, 1441.
[10]	(a) Yang, Z.; Zhou, Y.; Li, H.; Lei, J.; Bing, P.; He, B.; Li, Y. Asian J. Org. Chem. 2022, 11, e202100656.
	(b) Shao, Q.; Wu, L.; Chen, J.; Gridnev, I. D.; Yang, G.; Xie, F.; Zhang, W. Adv. Synth. Catal. 2018, 360, 4625.
	(c) Laha, J. K.; Jethava, K. P. J. Org. Chem. 2017, 82, 3597.
[11]	(a) Hou, J.-C.; Cai, W.; Ji, H.-T.; Ou, L.-J.; He, W.-M. Chin. Chem. Lett. 2025, 36, 110469.
	(b) Zhang, S.; Zhang, J.; Ling, X.; Zhao, Y.; Ma, Y.; Sun, P. Chin. J. Chem. 2024, 42, 1481.
	(c) Jia, H.; Li, N.; Tang, C.; Wang, Y.; Xi, Y.; Liao, R.; Xu, W.; Wu, F.; Shen, X.; Zhai, H. Chin. J. Chem. 2024, 42, 505.
[12]	(a) Liu, S.-S.; Dong, W.-W.; Li, Z.-Z.; Zhang, Y.-Y.; Li, C.; Jiao, L.-Y. Acta Chim. Sinica 2025, 83, 479. (in Chinese)
	(刘珊珊, 董微微, 李珍珍, 张瑶瑶, 李超, 焦林郁, 化学学报, 2025, 83, 479.)
	(b) Chen, J.-Q.; Zhu, G.-G.; Wu, J. Acta Chim. Sinica 2024, 82, 190. (in Chinese)
	(陈健强, 朱钢国, 吴劼, 化学学报, 2024, 82, 190.)
	(c) Yang, L.-Y.; Li, Y.; Shu, C. Acta Chim. Sinica 2024, 82, 171. (in Chinese)
	(杨铃悦, 李赟婷, 舒超, 化学学报, 2024, 82, 171.)
[13]	Pham, Q. H.; Hyland, C. J. T.; Pyne, S. G. Org. Biomol. Chem. 2020, 18, 7467.
[14]	Wang, J.; Liu, X.; Wu, Z.; Li, F.; Qin, T.; Zhang, S.; Kong, W.; Liu, L. Chin. Chem. Lett. 2021, 32, 2777.
[15]	Wang, J.; Liu, X.; Wu, Z.; Li, F.; Zhang, M.-L.; Mi, Y.; Wei, J.; Zhou, Y.; Liu, L. Chem. Commun. 2021, 57, 1506.
[16]	Wang, J.; Qin, Y.; Cui, K.; Li, X.; Cui, M.; Cao, S.; Zhang, L.; Shen, Q.; Wang, T.; Li, F. Chem. Commun. 2025, 61, 3359.
[17]	Liu, J.; Li, X.; Chen, G.; Luo, H. Adv. Synth. Catal. 2025, 367, e202500002.
[18]	(a) Li, Z.; Jin, J.; Huang, S. Chin. J. Org. Chem. 2020, 40, 563. (in Chinese)
	(李祯龙, 金健, 黄莎华, 有机化学, 2020, 40, 563.)
	(b) Shi, L.; Li, T.; Zhang, W.; Hu, W.; Zhu, X.; Lu, Y.; Mei, G.-J. Green. Synth. Catal. 2024, 5, 277.
	(c) Zhang, L.; Zheng, K.; Zhang, P.; Jiang, M.; Shen, J.; Chen, C.; Shen, C. Green. Synth. Catal. 2024, 5, 51.
	(d) Cannalire, R.; Pelliccia, S.; Sancineto, L.; Novellino, E.; Tron, G. C.; Giustiniano, M. Chem. Soc. Rev. 2021, 50, 766.
[19]	Holmberg-Douglas, N.; Nicewicz, D. A. Chem. Rev. 2022, 122, 1925.
[20]	Wang, J.; Li, F.; Liu, K.; Li, C.; Cao, S.; Wu, Y.; Yuan, Y.; Teng, F.; Wang, T.; Zhou, Y. Green. Synth. Catal. 2024, 5, 315.
[21]	Song, H.-Y.; Xiao, F.; Jiang, J.; Wu, C.; Ji, H.-T.; Lu, Y.-H.; Wang, K.-L.; He, W.-M. Chin. Chem. Lett. 2023, 34, 108509.
[22]	(a) Chen, X.; Wang, J.; Chai, Y.; Zhang, Z.; Zhu, Y. Adv. Mater. 2021, 33, 2007479.
	(b) Song, H.-Y.; Jiang, J.; Wu, C.; Hou, J.-C.; Lu, Y.-H.; Wang, K.-L.; Yang, T.-B.; He, W.-M. Green Chem. 2023, 25, 3292.
	(c) Ji, H.-T.; Wang, J.-S.; Shang, J.-F.; Li, R.-Q.; Yang, Z.; Zhu, H.-T.; He, W.-M. Org. Biomol. Chem. 2026, 24, 829-833.
[23]	(a) Ji, H.-T.; Lu, Y.-H.; Liu, Y.-T.; Huang, Y.-L.; Tian, J.-F.; Liu, F.; Zeng, Y.-Y.; Yang, H.-Y.; Zhang, Y.-H.; He, W.-M. Chin. Chem. Lett. 2025, 36, 110568.
	(b) Peng, Q.-H.; Peng, J.; Cai, Y.-L.; Wang, Z.-L.; Yi, R.-N.; Shen, C.; He, W.-M. Acta Chim. Sinica 2025, 83, 1013. (in Chinese)
	(彭琼慧, 彭佳, 蔡迎丽, 王祖利, 易荣楠, 沈超, 何卫民, 化学学报, 2025, 83, 1013.)
[24]	Zhou, B.; Dong, M.; Wang, W.; Yu, S.; Yue, H.; Wei, W.; Yi, D. J. Org. Chem. 2024, 89, 18337.
[25]	Zhang, J.; Li, X.; Liao, L.; Liu, H.; Luo, H. Adv. Synth. Catal. 2023, 365, 4544.
[26]	Fang, L.; Yu, J.; Yu, Z.; Tong, F.; Zhang, C.; Hu, D.; Zhang, J. Q.; Ren, H. J. Org. Chem. 2023, 88, 17249.
[27]	Hu, X.; Sun, R.; Tian, Y.; Xu, X.; Zhu, Y.; Liu, H.; Liu, D.; Zhang, L. Adv. Synth. Catal. 2025, 367, e202401430.
[28]	Tang, Z.; Pi, C.; Wu, Y.; Cui, X. Green. Synth. Catal. 2024, 5, 31.
[29]	Shi, A.; Sun, K.; Chen, X.; Qu, L.; Zhao, Y.; Yu, B. Org. Lett. 2022, 24, 299.
[30]	Shi, A.; Sun, K.; Wu, Y.; Xiang, P.; Krylov, I. B.; Terent'ev, A. O.; Chen, X.; Yu, B. J. Catal. 2022, 415, 28.
[31]	Gui, Q.-W.; Teng, F.; Li, Z.-C.; Xiong, Z.-Y.; Jin, X.-F.; Lin, Y.-W.; Cao, Z.; He, W.-M. Chin. Chem. Lett. 2021, 32, 1907.
[32]	(a) Liu, B.; Liu, M.; Wu, Z.; Zhang, M.; Meng, F.; Wang, Y.; Du, N.; Xu, H. J. Mol. Liq. 2024, 410, 125613.
	(b) Liu, B.; Yin, S.; Wu, X.; Wu, Z.; Lv, D.; Wang, Y.; Li, Z. Colloid Surf.,A 2025, 719, 136986.
[33]	Lu, Y.-H.; Wu, C.; Hou, J.-C.; Wu, Z.-L.; Zhou, M.-H.; Huang, X.-J.; He, W.-M. ACS Catal. 2023, 13, 13071.
[34]	Liu, M.-Y.; Jiang, J.; Ji, H.-T.; Wang, K.-L.; Huang, X.-J.; Wu, C.; He, W.-M. J. Catal. 2024, 434, 115509.
[35]	Wang, X.; Shi, A.; Huang, X.-Q.; Chen, X.; Li, T.; Qu, L.; Yu, B. Org. Biomol. Chem. 2022, 20, 3798.
[36]	(a) Wu, Y.; Chen, J.-Y.; Ning, J.; Jiang, X.; Deng, J.; Deng, Y.; Xu, R.; He, W.-M. Green Chem. 2021, 23, 3950.
	(b) Wen, Y.-C.; Hou, J.-C.; Zhou, Q.; Wang, S.-H.; Jiang, J.; Yang, Z.; Zhu, H.-T.; Wang, Z.-L.; He, W.-M. Chin. Chem. Lett. 2025, 36, 111795.
[37]	Lu, Y.-H.; Mu, S.-Y.; Li, H.-X.; Jiang, J.; Wu, C.; Zhou, M.-H.; Ouyang, W.-T.; He, W.-M. Green Chem. 2023, 25, 5539.
[38]	Song, H.-Y.; Jiang, J.; Song, Y.-H.; Zhou, M.-H.; Wu, C.; Chen, X.; He, W.-M. Chin. Chem. Lett. 2024, 35, 109246.
[39]	Zhang, J.; Li, X.; Chen, G.; Liu, H.; Luo, H. Chem. Commun. 2025, 61, 1669.
[40]	Kim, Y.; Kim, S. Y.; Kim, S. G. J. Org. Chem. 2023, 88, 1113.
[41]	Liu, X.; Wang, J.; Wu, Z.; Li, F.; Gao, K.; Peng, F.; Wang, J.; Shen, R.; Zhou, Y.; Liu, L. Org. Biomol. Chem. 2021, 19, 3595.
[42]	(a) Wang, H.-X.; Li, Z.-H.; Li, W.-W.; Qu, G.-R.; Yang, Q.-L.; Guo, H.-M. Green Chem. 2022, 24, 8377.
	(b) Peng, Q.-H.; Li, N.-B.; Hou, J.-C.; He, C.-J.; Yang, Y.-X.; Zhuang, C.-L.; Ou, L.-J.; Yuan, M.; He, W.-M. Chin. Chem. Lett. 2025, 36, 111402.
[43]	(a) Wu, C.; Wu, S.; Huang, Q.; Sun, K.; Huang, X.; Wang, J.; Yu, B. Chin. Chem. Lett. 2025, 36, 110250.
	(b) Ji, H.-T.; Yi, Y.-T.; Zhou, M.-H.; Luo, Q.-X.; Jiang, J.; He, W.-M. Asian J. Org. Chem. 2025, 14, e202400413.
[44]	Wu, Z.; Wang, J.; Li, F.; Zhai, H.; Ding, Q.; Han, D.; Cao, Z. Tetrahedron Lett. 2022, 91, 153642.
[45]	Goud, S. B.; Guin, S.; Prakash, M.; Samanta, S. Org. Biomol. Chem. 2022, 20, 352.
[46]	Liu, X.; Yu, X.; Jin, S.; Yin, Y.; Hao, L.; Ji, Y. Org. Lett. 2025, 46, 12801.

N-磺酰基酮亚胺的C—H官能团化研究进展