Photoexcitation-Enabled C(sp2)—N Coupling of Aryl Halides with Sulfonamides Catalyzed by Earth-Abundant Nickel

doi:10.6023/cjoc202511014

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (7): 2835-2852.DOI: 10.6023/cjoc202511014 Previous Articles Next Articles

ARTICLE

光激发丰产金属镍催化卤代芳烃与磺酰胺的C(sp²)—N偶联反应

王力卓, 刘馨忆, 宋戈洋^*(), 石晓莉, 薛东^*()

陕西师范大学化学化工学院应用表面与胶体化学教育部重点实验室西安 710119

收稿日期:2025-11-21 修回日期:2025-12-22 发布日期:2026-02-11
基金资助:
国家自然科学基金(22171174); 国家自然科学基金(22471150); 国家自然科学基金(22402113); 中央高校基本科研业务费(GK202406026); 中央高校基本科研业务费(GK202505023); 中央高校基本科研业务费(GK202505026); 陕西省创新能力支撑计划(2023-CX-TD-28); 陕西省化学与生物基础科学研究(22JHZ0027); 陕西省自然科学基金(2024JC-YBQN-0075); 天然药物及仿生药物国家重点实验室基金(K202437); 及陕西省重点研发计划(2024CY-JJQ-26)

Photoexcitation-Enabled C(sp²)—N Coupling of Aryl Halides with Sulfonamides Catalyzed by Earth-Abundant Nickel

Lizhuo Wang, Xinyi Liu, Geyang Song^*(), Xiaoli Shi, Dong Xue^*()

Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119

Received:2025-11-21 Revised:2025-12-22 Published:2026-02-11
Contact: *E-mail: songgeyang@snnu.edu.cn;xuedong_welcome@snnu.edu.cn
Supported by:
National Natural Science Foundation of China(22171174); National Natural Science Foundation of China(22471150); National Natural Science Foundation of China(22402113); Fundamental Research Funds for the Central Universities(GK202406026); Fundamental Research Funds for the Central Universities(GK202505023); Fundamental Research Funds for the Central Universities(GK202505026); Innovation Capability Support Program of Shaanxi Province(2023-CX-TD-28); Fundamental Science Research Project for Chemistry and Biology of Shaanxi Province(22JHZ0027); Natural Science Foundation of Shaanxi Province(2024JC-YBQN-0075); State Key Laboratory of Natural and Biomimetic Drugs(K202437); Key Research and Development Program of Shaanxi Province(2024CY-JJQ-26)

1. .pdf(16625KB)

Abstract

Sulfonamide compounds have attracted considerable attention in medicinal and synthetic chemistry due to their diverse biological activities, distinctive reactivity, and potential pharmaceutical value. A mild and efficient method that requires no external photosensitizer was developed to achieve the C(sp²)—N coupling of aryl halides with sulfonamide compounds under irradiation from 390~395 nm LEDs, catalyzed by an earth-abundant nickel catalyst. That method employs readily available nickel as the catalyst and soluble organic amines as bases, offering advantages such as easily accessible starting materials, mild reaction conditions, simple operation, broad substrate scope, and excellent functional-group tolerance. It can also be applied to late-stage modification of bioactive molecules. Even on the gram scale, the reaction maintains high efficiency and yield, providing a practical alternative route for the synthesis of important aryl sulfonamides. Mechanistic studies suggest that the reaction may proceed through a Ni(I)-Ni(III) catalytic cycle.

Key words: photocatalysis, nickel catalysis, aryl halide, C—N coupling reaction

Cite this article

Lizhuo Wang, Xinyi Liu, Geyang Song, Xiaoli Shi, Dong Xue. Photoexcitation-Enabled C(sp²)—N Coupling of Aryl Halides with Sulfonamides Catalyzed by Earth-Abundant Nickel[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2835-2852.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 8

References 36

[1]	Apaydın, S.; Török, M. Bioorg. Med. Chem. Lett. 2019, 29, 2042. doi: 10.1016/j.bmcl.2019.06.041
[2]	Haensch, V. G.; Neuwirth, T.; Hertweck, C. Chem.-Eur. J. 2019, 25, 16068. doi: 10.1002/chem.201903582
[3]	Fier, P. S.; Maloney, K. J. Am. Chem. Soc. 2019, 141, 1441. doi: 10.1021/jacs.8b11800
[4]	Fier, P. S.; Kim, S.; Maloney, K. M. J. Am. Chem. Soc. 2019, 141, 18416. doi: 10.1021/jacs.9b10985
[5]	Alejandro, G.-P.; Cornella, J. Angew. Chem., Int. Ed. 2019, 58, 18235. doi: 10.1002/anie.v58.50
[6]	Drews, J. Science 2000, 287,1960. doi: 10.1126/science.287.5460.1960 pmid: 10720314
[7]	Devendar, P.; Yang, G.-F. Top. Curr. Chem. 2017, 375, 82.
[8]	Caine, B. A.; Bronzato, M.; Popelier, L. A. Chem. Sci. 2019, 10, 6368. doi: 10.1039/c9sc01818b pmid: 31341593
[9]	Groote, P. De.; Devaux, J.; Godard, P. J. Polym. Sci., art B 2002, 40, 2208.
[10]	Wang, L.; Pan, X.; Liu, L. Dyes Pigm. 2008, 76, 636. doi: 10.1016/j.dyepig.2006.12.003
[11]	Wolfe, J. P.; Rennels, R. A.; Buchwald, S. L. Tetrahedron Lett. 1996, 52, 7525. doi: 10.1016/0040-4020(96)00266-9
[12]	Burton, G.; Cao, P.; Rivero, R. Org. Lett. 2003, 5, 4373. doi: 10.1021/ol035655u
[13]	Rosen, B. R.; Ruble, J. C.; Navarro, A. Org. Lett. 2011, 13, 2564. doi: 10.1021/ol200660s
[14]	Shekhar, S.; Dunn, T. B.; Cullen, S. C. J. Org. Chem. 2011, 76, 4552. doi: 10.1021/jo200443u
[15]	DeBergh, J. R.; Niljianskul, N.; Buchwald, S. L. J. Am. Chem. Soc. 2013, 135, 10638. doi: 10.1021/ja405949a pmid: 23837740
[16]	Laffoon, S. D.; Chan, V. S.; Shekhar, S. ACS Catal. 2019, 9, 11691. doi: 10.1021/acscatal.9b03012
[17]	Shavnya, A.; Coffey, S. B.; Mascitti, V. Org. Lett. 2013, 15, 6226. doi: 10.1021/ol403072r pmid: 24256546
[18]	Chan, D. M. T.; Monaco, K. L.; Winters, M. P. Tetrahedron Lett. 1998, 39, 2933. doi: 10.1016/S0040-4039(98)00503-6
[19]	Baffoe, J.; Hoe, M. Y.; Toure, B. B. Org. Lett. 2010, 12, 1532. doi: 10.1021/ol100263r
[20]	Vantourout, J. C.; Li, L.; Watson, A. J. B. ACS Catal. 2018, 8, 9560. doi: 10.1021/acscatal.8b03238
[21]	McGuire, R. T.; Simon, C. M.; Stradiotto, M. Angew. Chem., Int. Ed. 2020, 59, 8952. doi: 10.1002/anie.202002392 pmid: 32162451
[22]	Fu, Y.; Zhu, W.; Hu, Y. Org. Biomol. Chem. 2014, 12, 4295. doi: 10.1039/C4OB00638K
[23]	Twilton, J.; Le, C. Nat. Rev. Chem. 2017, 1, 0052. doi: 10.1038/s41570-017-0052
[24]	Tasker, S. Z.; Standley, E. A.; Jamison, T. F. Nature 2014, 509, 299. doi: 10.1038/nature13274
[25]	Kim, T.; McCarver, S. J.; MacMillan, D. W. C. Angew. Chem., Int. Ed. 2018, 57, 3488. doi: 10.1002/anie.v57.13
[26]	Corcoran, E. B.; Pirnot, M. T.; Lin, S. D. D. S.; Dirocco, D. A.; Davies, I. W.; Buchwald, S. L.; MacMillan, D. W. C. Science 2016, 353, 279. doi: 10.1126/science.aag0209 pmid: 27338703
[27]	Welin, E. R.; Le, C.; Rotondo, D. M. A.; McCusker, J. K.; MacMillan, D. W. C. Science 2017, 355, 380. doi: 10.1126/science.aal2490 pmid: 28126814
[28]	Zhou, Q.; Lu, F.; Liu, D.; Lu, L.; Xiao, W. Org. Chem. Front. 2018, 5, 3098. doi: 10.1039/C8QO00805A
[29]	Hang, H.; Wang, X.; Wang, J. Chin. J. Org. Chem. 2019, 39, 1 (in Chinese).
	(黄航, 王兮, 王剑波, 有机化学, 2019, 39, 1.) doi: 10.6023/cjoc201808030
[30]	Yang, L.; Lu, H.-H.; Lai, C.-H.; Li, G.; Zhang, W.; Cao, R.; Liu, F.; Wang, C.; Xiao, J.; Xue, D. Angew. Chem., Int. Ed. 2020, 59, 12714. doi: 10.1002/anie.202003359 pmid: 32281220
[31]	Li, G.; Yang, L.; Liu, J.-J.; Zhang, W.; Cao, R.; Wang, C.; Zhang, Z.; Xiao, J.; Xue, D. Angew. Chem., Int. Ed. 2021, 60, 5230. doi: 10.1002/anie.v60.10
[32]	Song, G.; Yang, L.; Li, J.-S.; Tang, W.-J.; Zhang, W.; Cao, R.; Wang, C.; Xiao, J.; Xue, D. Angew. Chem., Int. Ed. 2021, 60, 21536. doi: 10.1002/anie.v60.39
[33]	Song, G.; Nong, D.-Z.; Li, Q.; Yan, Y.; Li, G.; Fan, J.; Zhang, W.; Cao, R.; Wang, C.; Xiao, J.; Xue, D. ACS Catal. 2022, 12, 15590. doi: 10.1021/acscatal.2c04959
[34]	Song, G.; Li, Q.; Nong, D.-Z.; Song, J.; Li, G.; Wang, C.; Xiao, J.; Xue, D. Chem.-Eur. J. 2023, 29, e202300458. doi: 10.1002/chem.v29.37
[35]	Song, G.; Li, Q.; Song, J, Nong, D.-Z.; Dong, J.; Li, G.; Fan, J.; Wang, C.; Xiao, J.; Xue, D. Angew. Chem., Int. Ed. 2024, 63, e202314355. doi: 10.1002/anie.v63.6
[36]	Song, G.; Song, J.; Dong, J.; Li, G.; Fan, J.; Xue, D. Organometallics 2024, 43, 1706. doi: 10.1021/acs.organomet.3c00506

Entry	Deviation from the standard conditions	Yield/%
1	Standard conditions	92 (88)^b
2	NiCl₂	67
3	NiI₂	62
4	Ni(OAc)₂	38
5	NiBr₂•dme	79
6	NiBr₂	83
7	NiCl₂•dme	85
8	DABSO	7
9	BTMG	67
10	DIPEA	25
11	DBU	77
12	DMAP	9
13	K₂CO₃	N.R.
14	MeONa	N.R.
15	Blue LEDs (460~465 nm)	21
16	UV (365~370 nm)	N.R.
17	Green LEDs (530~535 nm)	N.R.
18	White LEDs	N.R.
19	Standard conditions, without ligand	13
20	Standard conditions, without Ni(cod)₂	N.R.
21	Standard conditions, without base	N.R.
22	Standard conditions, light, r.t.	N.R.
23	Standard conditions, without light, heat to 80 ℃	N.R.

Entry	Deviation from the standard conditions	Yield/%
1	Standard conditions	92 (88)^b
2	NiCl₂	67
3	NiI₂	62
4	Ni(OAc)₂	38
5	NiBr₂•dme	79
6	NiBr₂	83
7	NiCl₂•dme	85
8	DABSO	7
9	BTMG	67
10	DIPEA	25
11	DBU	77
12	DMAP	9
13	K₂CO₃	N.R.
14	MeONa	N.R.
15	Blue LEDs (460~465 nm)	21
16	UV (365~370 nm)	N.R.
17	Green LEDs (530~535 nm)	N.R.
18	White LEDs	N.R.
19	Standard conditions, without ligand	13
20	Standard conditions, without Ni(cod)₂	N.R.
21	Standard conditions, without base	N.R.
22	Standard conditions, light, r.t.	N.R.
23	Standard conditions, without light, heat to 80 ℃	N.R.

光激发丰产金属镍催化卤代芳烃与磺酰胺的C(sp²)—N偶联反应

Photoexcitation-Enabled C(sp²)—N Coupling of Aryl Halides with Sulfonamides Catalyzed by Earth-Abundant Nickel

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 8

References 36

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Dongping Wang, Yuxin Zhang, Shanshan Wei, Fengjiao Wang, Congjun Zhu. Recent Advances in Photoredox Nickel-Catalyzed Deoxygenative Coupling of Carboxylic Acids [J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2669-2682.
[2]	Yi Fang, Chuan Wang. Nickel-Catalyzed Allylic Defluorinative Cross-Electrophile Coupling of Trifluoromethyl-Substituted Alkenes with Alkyl Mesylates [J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2743-2750.
[3]	An Chen, Zeyi Wang, Wanmei Li, Jun Xu. Recent Advances in the Light-Driven One-Step Synthesis of Dual Carbon-Substituted Bicyclo[1.1.1]pentanes [J]. Chinese Journal of Organic Chemistry, 2026, 46(6): 2177-2192.
[4]	Ying Xu, Meilin Yang, Dapeng Cui, Miao Yu, Yingjie Liu. Research Progress on Defluorination Reactions [J]. Chinese Journal of Organic Chemistry, 2026, 46(5): 1962-1983.
[5]	Ziming Zhao, Jianfeng Zheng, Peiqiang Huang. Progress on the Photocatalytic Synthesis of Amines from Imines [J]. Chinese Journal of Organic Chemistry, 2026, 46(5): 1984-2001.
[6]	Xi Cheng, Yalin Li, Peng Wu, Min Su, Zixuan Zhang, Minjun Jiao, Xuefen Liu, Shuping Luo. Anthraquinone-Based Photosensitizers: Design, Synthesis and Application in Photocatalytic C(sp³)—H Oxidation [J]. Chinese Journal of Organic Chemistry, 2026, 46(5): 2104-2111.
[7]	Xinyi Hou, Tongtong Shi, Zejiang Li, Qinghao Dong, Kai Sun, Xin Wang. Visible-Light-Induced Phosphorylation Cyclization to Phosphorylated Indole-Fused Diazepines [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1776-1787.
[8]	Jingfei Zheng, Qiyan Lv, Kai Sun, Xiaolan Chen, Lingbo Qu, Jinquan Wang, Bing Yu. Recent Advances in Functionalization of 6-Azauracils via Radical Reactions [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1603-1620.
[9]	Yuqing Zhao, Xianjin Zhu, Lingyu Shi, Mingyu Wei, Zihan Xu, Yongjia Shi, Xufeng Li, Daoshan Yang. Research Progress on the Ring-Opening Functionalization of Cyclic Sulfonium Salts [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1572-1602.
[10]	Shan Yang, Yasu Chen, Chen Zhu. Construction of N-Fused Heteroarenes via Radical-Mediated Functional Group Migration-Cyclization [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1739-1749.
[11]	Linyu Lu, Yutong Qi, Tinghui Zhang, Shengnan Jin, Zhongyan Cao, Hongwei Zhang. Recent Progress in Radical Mediated 1,2,n-Trifunctiona-lization of Olefins [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1540-1559.
[12]	Jianyang Dong, Dong Xue. Research Progress on the Functionalization of [1.1.1]Propellane via Radical Pathways [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1464-1480.
[13]	Lingxu Meng, Lin Shen, Xiangling Luo, Yumei Lin, Lei Gong. Design of Photoactive Cr- and Co-Based Complexes and Their Applications in Organic Synthesis [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1513-1528.
[14]	Ning Yu, Yuqiang Zhou, Ye Wei. Recent Advances in Photocatalytic Radical-Mediated Lactone Synthesis [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1222-1254.
[15]	Ziliang Yuan, Bingdong Li, Dinghai Wang. Visible-Light Induced Hydrophosphination of Olefins [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1677-1684.

光激发丰产金属镍催化卤代芳烃与磺酰胺的C(sp2)—N偶联反应