Synthesis of Nafimidone Derivatives by Visible-Light-Induced α-C—H Functionalization of Carbonyl

doi:10.6023/cjoc202406051

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (2): 677-685.DOI: 10.6023/cjoc202406051 Previous Articles Next Articles

ARTICLES

可见光介导的羰基α位C—H官能团化反应合成萘咪酮类衍生物

沈佳斌^a^,^b^,^c, 沈超^b, 章鹏飞^c^,^*()

a 天津大学化工学院天津 300072
b 浙江树人学院生物与环境工程学院杭州 310015
c 杭州师范大学材料与化学化工学院杭州 311121

收稿日期:2024-06-30 修回日期:2024-08-31 发布日期:2024-09-26
基金资助:
浙江省科技厅重点研发计划(2024C01203)

Synthesis of Nafimidone Derivatives by Visible-Light-Induced α-C—H Functionalization of Carbonyl

Jiabin Shen^a^,^b^,^c, Chao Shen^b, Pengfei Zhang^c()

a School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072
b College of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015
c College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121

Received:2024-06-30 Revised:2024-08-31 Published:2024-09-26
Contact: *E-mail: pfzhang@hznu.edu.cn
Supported by:
Key Research & Development Project of Science Technology Department of Zhejiang Province(2024C01203)

1. .pdf(6785KB)

Abstract

A universal and practical visible-light-induced α-functionalization of carbonyl compounds is demonstrated using Esoin Y as photocatalyst. This mild transformation provides an efficient and convenient approach for the synthesis of potentially bioactive nafimidone derivatives with operational simplicity, a broad substrate scope and high atom economy. The mechanistic studies reveal that a free radical pathway mechanism is responsible for this transformation.

Key words: visible-light catalysis, C—H functionalization, C—S coupling reaction, C—O coupling reaction

Cite this article

Jiabin Shen, Chao Shen, Pengfei Zhang. Synthesis of Nafimidone Derivatives by Visible-Light-Induced α-C—H Functionalization of Carbonyl[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 677-685.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

References 18

[1]	Acar, M. F.; Sari, S.; Dalkara, S. Drug Dev. Res. 2019, 80, 606.
[2]	Özdemir, Z.; Sari, S.; Karakurt, A.; Dalkara, S. Drug Dev. Res. 2019, 80, 269.
[3]	Sari, S.; Karakurt, A.; Uslu, H.; Kaynak, F. B.; Çalıs, Ü.; Dalkara, S. Eur. J. Med. Chem. 2016, 124, 407.
[4]	Yamada, K.; Yajima, O.; Yoshizawa, Y.; Oh, K. Bioorg. Med. Chem. 2013, 21, 2451.
[5]	Weitz, J. I.; Chan, N. C. Arterioscler., Thromb., Vasc. Biol. 2019, 39, 7.
[6]	Lu, X.; He, S.; Li, Q.; Yang, H.; Jiang, X.; Lin, H.; Chen, Y.; Qu, W.; Feng, F.; Bian, Y.; Zhou, Y.; Sun, H. Bioorg. Med. Chem. 2018, 26, 1665.
[7]	Macarini, A. F.; Sobrinho, T. U. C.; Rizzi, G. W.; Corrêa, R. Med. Chem. Res. 2019, 28, 1235. doi: 10.1007/s00044-019-02368-8
[8]	Rilatt, I.; Mirabel, E.; Le Grand, B.; Perez, M. Bioorg. Med. Chem. 2010, 20, 903.
[9]	(a) Ouyang, W.-T.; Jiang, J.; Jiang, Y.-F.; Li, T.; Liu, Y.-Y.; Ji, H.-T.; Ou, L.-J.; He, W.-M. Chin. Chem. Lett. 2024, 35, 110038.
	(b) Hou, J.-C.; Ji, H.-T.; Lu, Y.-H.; Wang, J.-S.; Xu, Y.-D.; Zeng, Y.-Y.; He, W.-M. Chin. Chem. Lett. 2024, 35, 109514.
	(c) Chen, X.; Ouyang, W.-T.; Li, X.; He, W.-M. Chin. J. Org. Chem. 2023, 43, 4213 (in Chinese).
	(陈祥, 欧阳文韬, 李潇, 何卫民, 有机化学, 2023, 43, 4213.) doi: 10.6023/cjoc202307026
	(d) Guo, Y.; Zhu, J.; Wang, Y.; Li, Y.; Hu, H.; Zhang, P.; Xu, J.; Li, W. ACS Catal. 2024, 14, 619.
	(e) Zhang, L.; Wang, Y.; Shen, J.; Xu, H.; Shen, C. Org. Chem. Front. 2024, 11, 2727.
	(f) Liu, Y.; Pang, Q.; Chen, B.; Zhu, Z.; Shen, J.; Zhang, P. Mol. Catal. 2024, 569, 114592.
	(g) Yi, R.-N.; He, W.-M. Chin. Chem. Lett. 2024, 35, 110194.
[10]	(a) Li, L.; Pang, Q.; Chen, B.; Liu, Y.; Zhao, Y.; Wu, J.; Ge, K.; Shen, J.; Zhang, P. Org. Lett. 2024, 26, 7060.
	(b) Xu, J.; Zhang, Y.; Xu, R.; Wang, Y.; Shen, J.; Li, W. Org. Chem. Front. 2024, 11, 5122.
	(c) Shen, J.; Yang, Y.; Chen, C.; Xu, H.; Shen, C.; Zhang, P. Org. Chem. Front. 2024, 11, 1758.
	(d) Yi, R.; He, W. Chin. J. Org. Chem. 2024, 44, 1035 (in Chinese).
	(易荣楠, 何卫民, 有机化学, 2024, 44, 1035.) doi: 10.6023/cjoc202400014
	(e) Ma, C.; Luo, H.; Zhang, F.; Guo, D.; Chen, S.; Wang, F. Chin. J. Org. Chem. 2024, 44, 216 (in Chinese).
	(马翠云, 罗海澜, 张福华, 郭丹, 陈树兴, 王飞, 有机化学, 2024, 44, 216.) doi: 10.6023/cjoc202304028
	(f) Xu, J.; Hong, Y.; Xu, R.; Wang, Y.; Guo, Y.; Shen, J.; Zhao, Y.; Li, W. Org. Chem. Front. 2024, 11, 6166.
[11]	Tian, H.; Xu, W.; Liu, Y.; Wang, Q. Org. Lett. 2020, 22, 5005. doi: 10.1021/acs.orglett.0c01574 pmid: 32610920
[12]	Wang, J.; Ye, Y.; Sang, T.; Zhou, C.; Bao, X.; Yuan, Y.; Huo, C. Org. Lett. 2022, 24, 7577.
[13]	Wang, Y.-L.; Zhang, T.-X.; Zhang, X.-M.; Sun, H.-Y.; Leng, J.-Y.; Li, Y.-M. Chin. J. Org. Chem. 2023, 43, 4284 (in Chinese).
	(王永玲, 张铁欣, 张栩铭, 孙晗扬, 冷津瑶, 李亚明, 有机化学, 2023, 43, 4284.) doi: 10.6023/cjoc202304020
[14]	Shen, J.; Wang, Z.; Zhang, Y.; Xu, J.; Shen, C.; Zhang, P. Org. Chem. Front. 2023, 10, 605.
[15]	(a) Wang, Z.; Hu, L.; Zhao, M.; Dai, L.; Hrynsphan, D.; Tatsiana, S.; Chen, J. BioChar 2022, 4, 28.
	(b) Lv, S.; Zheng, F.; Wang, Z.; Hayat, K.; Veiga, M. C.; Kennes, C.; Chen, J. Sci. Total Environ. 2024, 908, 168339.
	(c) Guo, T.; Yue, H.; Ma, C.; Li, S.; Chen, J.; Li, W.; Zhao, J. Biorem. J. 2022, 26, 171.
	(d) Yao, J.; Mei, Y.; Yuan, B.; Zheng, F.; Wang, Z.; Chen, J. Environ. Res. 2024, 241, 117613.
	(e) Wang, Z.; Chen, C.; Liu, H.; Hrynshpan, D.; Savitskaya, T.; Chen, J.; Chen, J. Ecotoxicol. Environ. Saf. 2019, 183, 109507.
	(f) Wang, Z.; Fu, W.; Hu, L.; Zhao, M.; Guo, T.; Hrynsphan, D.; Tatsiana, S.; Chen, J. Sci. Total Environ. 2021, 781, 146686.
	(g) Wang, Z.; Chen, C.; Liu, H.; Hrynshpan, D.; Savitskaya, T.; Chen, J.; Chen, J. Sci. Total Environ. 2020, 708, 135063.
	(h) Wang, Z.; Dai, L.; Yao, J.; Guo, T.; Hrynsphan, D.; Tatsiana, S.; Chen, J. Chemosphere 2021, 281, 130718.
[16]	Yuan, P.-F.; Zhang, Q.-B.; Jin, X.-L.; Lei, W.-L.; Wu, L.-Z.; Liu, Q. Green Chem. 2018, 20, 5464.
[17]	(a) Shen, J.; Wang, Z.; Zhang, Y.; Xu, J.; Liu, X.; Shen, C.; Zhang, P. Org. Lett. 2022, 24, 3614.
	(b) Shen, J.; Wang, Z.; Shen, C.; Zhang, P. Mol. Catal. 2023, 537, 112950.
	(c) Wang, Z.; Chen, B.; Pang, Q.; Xu, J.; Shen, J.; Xu, J.; Li, W. Mol. Catal. 2024, 559, 114060.
	(d) Wang, Z.; Li, J.; Liu, Y.; Chen, Q.; Zhang, P.; Wu, J. Mol. Catal. 2023, 540, 113038.
[18]	(a) Shen, J.; Xu, J.; He, L.; Liang, C.; Li, W. Chin. Chem. Lett. 2022, 33, 1227.
	(b) Shen, J.; Xu, J.; He, L.; Ouyang, Y.; Huang, L.; Li, W.; Zhu, Q. Zhang, P. Org. Lett. 2021, 23, 1204.
	(c) Liang, C.; Wang, Z.; Chen, Q.; Wu, J.; Zhang, P.; Shen, J. Mol. Catal. 2024, 558, 114024.
	(d) Li, L.; Liu, Y.; Li, J.; Chen, Q.; Zhang, P.; Shen, J.; Wu, J. Adv. Synth. Catal. 2023, 365, 3112.
	(e) Zhu, J.; Hong, Y.; Wang, Y.; Guo, Y.; Zhang, Y.; Ni, Z.; Li, W.; Xu, J. ACS Catal. 2024, 14, 6247.

Entry	Metal-catalyst	Photocatalyst	Base	Solvent	Yield^b/%
1	CuI	Fluorescein	Et₃N	MeCN	65
2	CuCl	Fluorescein	Et₃N	MeCN	54
3	CuCl₂	Fluorescein	Et₃N	MeCN	43
4	Cu₂O	Fluorescein	Et₃N	MeCN	14
5	CuO	Fluorescein	Et₃N	MeCN	17
6	—	Fluorescein	Et₃N	MeCN	Trace
7	CuI	Rose Bengal	Et₃N	MeCN	54
8	CuI	9-Fluorenone	Et₃N	MeCN	71
9	CuI	Mes-Acr^＋	Et₃N	MeCN	43
10	CuI	—	Et₃N	MeCN	Trace
11	CuI	Eosin Y	Et₃N	MeCN	76
12	CuI	Eosin Y	DMAP	MeCN	87
13	CuI	Eosin Y	NaOH	MeCN	64
14	CuI	Eosin Y	KOH	MeCN	67
15	CuI	Eosin Y	K₂HPO₄	MeCN	51
16	CuI	Eosin Y	NaHCO₃	MeCN	47
17	CuI	Eosin Y	DMAP	THF	52
18	CuI	Eosin Y	DMAP	DCE	63
19	CuI	Eosin Y	DMAP	DMSO	74
20	CuI	Eosin Y	DMAP	DMF	68
21	CuI	Eosin Y	DMAP	Dioxane	56
22^c	CuI	Eosin Y	DMAP	MeCN	86
23^d	CuI	Eosin Y	DMAP	MeCN	52
24^e	CuI	Eosin Y	DMAP	MeCN	87
25^f	CuI	Eosin Y	DMAP	MeCN	64
26^g	CuI	Eosin Y	DMAP	MeCN	87
27^h	CuI	Eosin Y	DMAP	MeCN	61
28ⁱ	CuI	Eosin Y	DMAP	MeCN	Trace
29^j	CuI	Eosin Y	DMAP	MeCN	Trace

Entry	Metal-catalyst	Photocatalyst	Base	Solvent	Yield^b/%
1	CuI	Fluorescein	Et₃N	MeCN	65
2	CuCl	Fluorescein	Et₃N	MeCN	54
3	CuCl₂	Fluorescein	Et₃N	MeCN	43
4	Cu₂O	Fluorescein	Et₃N	MeCN	14
5	CuO	Fluorescein	Et₃N	MeCN	17
6	—	Fluorescein	Et₃N	MeCN	Trace
7	CuI	Rose Bengal	Et₃N	MeCN	54
8	CuI	9-Fluorenone	Et₃N	MeCN	71
9	CuI	Mes-Acr^＋	Et₃N	MeCN	43
10	CuI	—	Et₃N	MeCN	Trace
11	CuI	Eosin Y	Et₃N	MeCN	76
12	CuI	Eosin Y	DMAP	MeCN	87
13	CuI	Eosin Y	NaOH	MeCN	64
14	CuI	Eosin Y	KOH	MeCN	67
15	CuI	Eosin Y	K₂HPO₄	MeCN	51
16	CuI	Eosin Y	NaHCO₃	MeCN	47
17	CuI	Eosin Y	DMAP	THF	52
18	CuI	Eosin Y	DMAP	DCE	63
19	CuI	Eosin Y	DMAP	DMSO	74
20	CuI	Eosin Y	DMAP	DMF	68
21	CuI	Eosin Y	DMAP	Dioxane	56
22^c	CuI	Eosin Y	DMAP	MeCN	86
23^d	CuI	Eosin Y	DMAP	MeCN	52
24^e	CuI	Eosin Y	DMAP	MeCN	87
25^f	CuI	Eosin Y	DMAP	MeCN	64
26^g	CuI	Eosin Y	DMAP	MeCN	87
27^h	CuI	Eosin Y	DMAP	MeCN	61
28ⁱ	CuI	Eosin Y	DMAP	MeCN	Trace
29^j	CuI	Eosin Y	DMAP	MeCN	Trace

可见光介导的羰基α位C—H官能团化反应合成萘咪酮类衍生物

Synthesis of Nafimidone Derivatives by Visible-Light-Induced α-C—H Functionalization of Carbonyl

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 7

References 18

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Yongmei Li, Liangbo Sun, Kun Xu, Chengchu Zeng. Recent Advances toward Electro- and Electrophotochemical 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-Catalyzed C—H/C—F Bonds Functionalization [J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 668-676.
[2]	Jihui Gao, Chuan He. X-Type Silyl Ligands Mediated C—H Functionalization Reactions [J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 641-654.
[3]	Yu Lin, Haifeng Fu, Hua Cao, Xiang Liu. Vinylene Carbonate: A Versatile Synthon in Organic Synthetic Chemistry [J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2147-2173.
[4]	Yanhua Fu, Chang Xu, Chao Zhang, Yisha Wang, Gaofeng Feng. Visible-Light Induced Iron-Catalyzed Hydroxymethylation of N-Heterocycles [J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2265-2273.
[5]	Xiangxue Cao, Yahui Jia, Shiji Yin, Liang Xu, Yu Wei, Huanhuan Song. Visible-Light-Induced C—C Bond Cleavage of Dihydroquinazolinones with Trifluoromethyl-Substituted Olefins Defluorinated Alkylation Reactions [J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1549-1557.
[6]	Aman Hasil, Rui Chang, Juntao Ye. Recent Advances on C—H Functionalization via Oxidative Electrophotocatalysis [J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 728-747.
[7]	Hui Xu, Huixian Jiang, Lei Kan, Pei Xu, Xu Zhu. Visible-Light-Induced Selective Hydrocarboxylation of Alkynes with Formate [J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3241-3248.
[8]	Jianghu Dong, Liangming Xuan, Chi Wang, Chenxi Zhao, Haifeng Wang, Qiongjiao Yan, Wei Wang, Fen'er Chen. Recent Advances in Visible-Light-Induced C(3)—H Functionalization of Quinoxalinones under Transition-Metal-Free or Photocatalyst-Free [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 111-136.
[9]	Hong'en Tong, Hongyu Guo, Rong Zhou. Progress on Visible-Light Promoted Addition Reactions of Inert C—H Bonds to Carbonyls [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 54-69.
[10]	Xiaoping Xu, Yifei Zhang, Xiaoyu Mo, Jun Jiang. Rh-Catalyzed C—H Functionalization Reaction between 3-Diazoindolin-2-imines and Pyrazolones for the Construction of 3-Pyrazolyl Indoles [J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2519-2527.
[11]	Sining Qin. Research Progress in C—S Coupling Reactions of Aryl Halides [J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3761-3783.
[12]	Ning Nan, Shuang Wu, Jinghao Qin, Jinheng Li. State-of-Art Advances on Silylation-Initiated Annulation Reactions [J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3414-3453.
[13]	Zhentao Pan, Tong Liu, Yongmin Ma, Jianbo Yan, Ya-Jun Wang. Construction of Quinazolin(thi)ones by Brønsted Acid/Visible-Light Photoredox Relay Catalysis [J]. Chinese Journal of Organic Chemistry, 2022, 42(9): 2823-2831.
[14]	Xihui Yang, Haowei Gao, Jiale Yan, Lei Shi. Recent Progress in Radical-Mediated Si—H Functionalization of Silanes: An Effective Strategy for the Synthesis of Organosilanes Containing C—Si Bond [J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4122-4151.
[15]	Xiaojing Tian, Zhenzhen Fan, Si Jiang, Zhiwei Li, Jiangsheng Li, Yuefei Zhang, Cuihong Lu, Weidong Liu. Metal-Free Synthesis of Benzimidazo[1,2-c]quinazolines from N-Cyanobenzimidazoles via Double C—H Functionalizations [J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3684-3692.