Electron Donor-Acceptor (EDA) Complexes Mediated Free Radicals Cyclization of N-Arylacrylamide with Arylthionium Salts

doi:10.6023/cjoc202412025

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (8): 2913-2922.DOI: 10.6023/cjoc202412025 Previous Articles Next Articles

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电子供体-受体复合物(EDA)介导N-芳基丙烯酰胺与芳基硫鎓盐的自由基环化反应

解人杰^a, 谢复开^b, 孙然^a^,^*(), 王欣^a, 王钰佳^a, 李蕾^a, 王贺^a^,^*()

^a 辽宁石油化工大学辽宁抚顺 113001
^b 中国科学院大连化学物理研究所辽宁大连 116021

收稿日期:2024-12-25 修回日期:2025-03-07 发布日期:2025-03-31
基金资助:
国家自然科学基金(21801105); 辽宁省教育厅基本科研(JYTMS20231433); 辽宁省教育厅基本科研(JYTMS20231451)

Electron Donor-Acceptor (EDA) Complexes Mediated Free Radicals Cyclization of N-Arylacrylamide with Arylthionium Salts

Renjie Xie^a, Fukai Xie^b, Ran Sun^a^,^*(), Xin Wang^a, Yujia Wang^a, Lei Li^a, He Wang^a^,^*()

^a Liaoning Petrochemical University, Fushun, Liaoning 113001
^b Dalian Institute of Chemical Physics, Dalian, Liaoning 116021

Received:2024-12-25 Revised:2025-03-07 Published:2025-03-31
Contact: *E-mail:hewang@lnpu.edu.cn;sunran@lnpu.edu.cn
Supported by:
National Natural Science Foundation of China(21801105); General Program of the Education Department of Liaoning Province(JYTMS20231433); General Program of the Education Department of Liaoning Province(JYTMS20231451)

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Abstract

A series of potentially bioactive indolones were synthesized under light irradiation via catalyst-free electron donor-acceptor (EDA) complexes formed between arylthionium salts and unsaturated arylamide compounds. The photoexcited EDA complex generated an aryl radical, which subsequently underwent radical addition followed by intramolecular cyclization to yield the desired products. The reaction exhibited high regioselectivity. Additionally, based on preliminary studies of the reaction mechanism, a plausible catalytic cycle for the tandem radical reaction has been proposed.

Key words: electron donor-acceptor complexes, photocatalyst-free, aryl thianthrenium salts, N-arylacrylamides, indolones

Cite this article

Renjie Xie, Fukai Xie, Ran Sun, Xin Wang, Yujia Wang, Lei Li, He Wang. Electron Donor-Acceptor (EDA) Complexes Mediated Free Radicals Cyclization of N-Arylacrylamide with Arylthionium Salts[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2913-2922.

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Fig. & Tab. 5

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Entry	Base (equiv.)	Solvent (V∶V)	Yield^b/%
1	K₂CO₃(2)	MeCN	48
2^c	K₂CO₃(2)	MeCN	20
3^d	K₂CO₃(2)	MeCN	Trace
4^e	K₂CO₃(2)	MeCN	46
5^f	K₂CO₃(2)	MeCN	47
6	None	MeCN	40
7	K₂CO₃(2)	DMF	41
8	K₂CO₃(2)	THF	42
9	K₂CO₃(2)	DCM	31
10	K₂CO₃(2)	Toluene	41
11	K₂CO₃(2)	EtOH	43
12	K₂CO₃(2)	DMSO	47
13	K₂CO₃(2)	1,4-Dioxane	29
14	K₂CO₃(2)	MeCN/DMSO (1∶1)	43
15	K₂CO₃(2)	MeCN/DMSO (1∶4)	52
16	K₂CO₃(2)	MeCN/DMSO (1∶9)	47
17	Li₂CO₃(2)	MeCN/DMSO (1∶4)	44
18	Na₂CO₃(2)	MeCN/DMSO (1∶4)	46
19	Cs₂CO₃(2)	MeCN/DMSO (1∶4)	40
20	HCOOK (2)	MeCN/DMSO (1∶4)	28
21	2,6-Lutidine (2)	MeCN/DMSO (1∶4)	51
22	DBU (2)	MeCN/DMSO (1∶4)	33
23	DABCO (2)	MeCN/DMSO (1∶4)	39
24	NEt₃(2)	MeCN/DMSO (1∶4)	27
25^g	K₂CO₃(2)	MeCN/DMSO (1∶4)	58
26^h	K₂CO₃(2)	MeCN/DMSO (1∶4)	58
27ⁱ	K₂CO₃(2)	MeCN/DMSO (1∶4)	57
28^j	K₂CO₃(2)	MeCN/DMSO (1∶4)	56
29^g	K₂CO₃ (0.05)	MeCN/DMSO (1∶4)	51
30^g	K₂CO₃ (1)	MeCN/DMSO (1∶4)	54
31^g	K₂CO₃ (1.5)	MeCN/DMSO (1∶4)	57
32^g	K₂CO₃ (2.5)	MeCN/DMSO (1∶4)	58
33^g^,^k	Na₂CO₃(2)	MeCN/DMSO (1∶4)	58
34^g^,^l	K₂CO₃(2)	MeCN/DMSO (1∶4)	37

Entry	Base (equiv.)	Solvent (V∶V)	Yield^b/%
1	K₂CO₃(2)	MeCN	48
2^c	K₂CO₃(2)	MeCN	20
3^d	K₂CO₃(2)	MeCN	Trace
4^e	K₂CO₃(2)	MeCN	46
5^f	K₂CO₃(2)	MeCN	47
6	None	MeCN	40
7	K₂CO₃(2)	DMF	41
8	K₂CO₃(2)	THF	42
9	K₂CO₃(2)	DCM	31
10	K₂CO₃(2)	Toluene	41
11	K₂CO₃(2)	EtOH	43
12	K₂CO₃(2)	DMSO	47
13	K₂CO₃(2)	1,4-Dioxane	29
14	K₂CO₃(2)	MeCN/DMSO (1∶1)	43
15	K₂CO₃(2)	MeCN/DMSO (1∶4)	52
16	K₂CO₃(2)	MeCN/DMSO (1∶9)	47
17	Li₂CO₃(2)	MeCN/DMSO (1∶4)	44
18	Na₂CO₃(2)	MeCN/DMSO (1∶4)	46
19	Cs₂CO₃(2)	MeCN/DMSO (1∶4)	40
20	HCOOK (2)	MeCN/DMSO (1∶4)	28
21	2,6-Lutidine (2)	MeCN/DMSO (1∶4)	51
22	DBU (2)	MeCN/DMSO (1∶4)	33
23	DABCO (2)	MeCN/DMSO (1∶4)	39
24	NEt₃(2)	MeCN/DMSO (1∶4)	27
25^g	K₂CO₃(2)	MeCN/DMSO (1∶4)	58
26^h	K₂CO₃(2)	MeCN/DMSO (1∶4)	58
27ⁱ	K₂CO₃(2)	MeCN/DMSO (1∶4)	57
28^j	K₂CO₃(2)	MeCN/DMSO (1∶4)	56
29^g	K₂CO₃ (0.05)	MeCN/DMSO (1∶4)	51
30^g	K₂CO₃ (1)	MeCN/DMSO (1∶4)	54
31^g	K₂CO₃ (1.5)	MeCN/DMSO (1∶4)	57
32^g	K₂CO₃ (2.5)	MeCN/DMSO (1∶4)	58
33^g^,^k	Na₂CO₃(2)	MeCN/DMSO (1∶4)	58
34^g^,^l	K₂CO₃(2)	MeCN/DMSO (1∶4)	37

电子供体-受体复合物(EDA)介导N-芳基丙烯酰胺与芳基硫鎓盐的自由基环化反应

Electron Donor-Acceptor (EDA) Complexes Mediated Free Radicals Cyclization of N-Arylacrylamide with Arylthionium Salts

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