Metal-Free Synthesis of Benzimidazo[1,2-c]quinazolines from N-Cyanobenzimidazoles via Double C—H Functionalizations

doi:10.6023/cjoc202205030

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (11): 3684-3692.DOI: 10.6023/cjoc202205030 Previous Articles Next Articles

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无金属催化的双C—H功能化N-氰基苯并咪唑合成苯并咪唑并[1,2-c]喹唑啉衍生物

田晓京^a, 范禛禛^a, 姜思^a, 李志伟^a^,^*(), 李江胜^a^,^*(), 张跃飞^a, 卢翠红^a, 刘卫东^b

^a长沙理工大学化学化工学院细胞化学湖南省重点实验室长沙 410114
^b湖南化工研究院国家农药创制工程技术研究中心长沙 410007

收稿日期:2022-05-18 修回日期:2022-07-08 发布日期:2022-08-10
通讯作者: 李志伟, 李江胜
基金资助:
农用化学品湖南省重点实验室开放课题(HKLA-OF2020001); 长沙市自然科学基金(kq2202185); 长沙市自然科学基金(2202184); 国家级大学生创新创业训练计划(202010536017)

Metal-Free Synthesis of Benzimidazo[1,2-c]quinazolines from N-Cyanobenzimidazoles via Double C—H Functionalizations

Xiaojing Tian^a, Zhenzhen Fan^a, Si Jiang^a, Zhiwei Li^a(), Jiangsheng Li^a(), Yuefei Zhang^a, Cuihong Lu^a, Weidong Liu^b

^aHunan Provincial Key Laboratory of CytoChemistry, School of Chemistry and Chemical Engineering, Changsha University of Science & Technology, Changsha 410114
^bNational Engineering Research Center for Agrochemicals, Hunan Research Institute of Chemical Industry, Changsha 410007

Received:2022-05-18 Revised:2022-07-08 Published:2022-08-10
Contact: Zhiwei Li, Jiangsheng Li
Supported by:
Hunan Provincial Key Laboratory of Agricultural Chemicals(HKLA-OF2020001); Changsha Municipal Natural Science Foundation(kq2202185); Changsha Municipal Natural Science Foundation(2202184); National Undergraduate Training Programs for Innovation and Entrepreneurship of China(202010536017)

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Abstract

A green and efficient method for synthesis of privileged benzimidazo[1,2-c]quinazoline scaffolds is developed through the double C—H functionalizations mediated by peroxides under metal-free conditions without any additives. This protocol undergoes a radical cascade cyclization process involving the relay between C-centered radicals and N-centered radicals and is well applicable to a variety of cyclic (thio)ethers, glycol ethers and cyclic alkanes. Noteworthily, the title compounds display significant insecticidal and fungicidal activities, especially to armyworm.

Key words: double C—H functionalization, radical cascade cyclization, cyanamide, benzimidazole, quinazoline

Cite this article

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.

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Entry	Variation from general conditions	Isolated yield/%
1	none	85
2	DTBP	83
3	BPO	58
4	125 ℃	87
5	130 ℃	86
6	1.5 equiv. at 125 ℃	84
7	2.3 equiv. at 125 ℃	86
8	5 h at 125 ℃	84
9	6 h at 125 ℃	90
10	7 h at 125 ℃	88

Entry	Variation from general conditions	Isolated yield/%
1	none	85
2	DTBP	83
3	BPO	58
4	125 ℃	87
5	130 ℃	86
6	1.5 equiv. at 125 ℃	84
7	2.3 equiv. at 125 ℃	86
8	5 h at 125 ℃	84
9	6 h at 125 ℃	90
10	7 h at 125 ℃	88

Compd.	Insecticidal activities			Fungicidal activities^d
Compd.	Armyworm^b	Aphid^c	Red spider^c	Phytophthora	Alternaria	Fusarium	Botrytis
3	100	64.09	0	52.83	70.00	3.17	44.90
12	100	85.64	0	60.19	59.47	10.92	43.12
18	100	93.07	6.30	85.97	84.70	25.78	69.20
24	100	95.32	2.16	93.54	88.13	12.70	82.86

Compd.	Insecticidal activities			Fungicidal activities^d
Compd.	Armyworm^b	Aphid^c	Red spider^c	Phytophthora	Alternaria	Fusarium	Botrytis
3	100	64.09	0	52.83	70.00	3.17	44.90
12	100	85.64	0	60.19	59.47	10.92	43.12
18	100	93.07	6.30	85.97	84.70	25.78	69.20
24	100	95.32	2.16	93.54	88.13	12.70	82.86

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无金属催化的双C—H功能化N-氰基苯并咪唑合成苯并咪唑并[1,2-c]喹唑啉衍生物

Metal-Free Synthesis of Benzimidazo[1,2-c]quinazolines from N-Cyanobenzimidazoles via Double C—H Functionalizations

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