I2/叔丁基过氧化氢促进烯丙基芳烃与二烷基甲酰胺氧化偶联合成α,β-不饱和酰胺

doi:10.6023/cjoc202502023

有机化学 ›› 2025, Vol. 45 ›› Issue (12): 4463-4467.DOI: 10.6023/cjoc202502023 上一篇下一篇

研究论文

I₂/叔丁基过氧化氢促进烯丙基芳烃与二烷基甲酰胺氧化偶联合成α,β-不饱和酰胺

苏任华^a, 肖朵朵^a^,^*(), 周鹏^a, 龙义福^b, 刘卫兵^a^,^*()

^a 广东石油化工学院化学学院广东茂名 525000
^b 深圳市豪龙新材料技术有限公司广东深圳 518110

收稿日期:2025-02-19 修回日期:2025-05-22 发布日期:2025-06-11
通讯作者: 肖朵朵, 刘卫兵
基金资助:
广东省普通高校青年创新人才(2023KQNCX043); 茂名绿色化工研究院杨帆计划(MMGCIRI-2022YFJH-Y-037); 国家自然科学基金(21602035); 广东省普通高等学校重点领域专项(2020ZDZX2054)

I₂/t-Butylhydroperoxide Mediated Oxidative Coupling of Allylbenze- nes with Dialkylformamides to Access α,β-Unsaturated Amides

Renhua Su^a, Duoduo Xiao^a^,^*(), Peng Zhou^a, Yifu Long^b, Weibing Liu^a^,^*()

^a College of Chemistry, Guangdong University of Petrochemical Technology, Maoming, Guangdong 525000
^b Shenzhen Haolong New Material Technology Co., Ltd., Shenzhen, Guangdong 518110

Received:2025-02-19 Revised:2025-05-22 Published:2025-06-11
Contact: Duoduo Xiao, Weibing Liu
Supported by:
Guangdong Provincial Junior Innovative Talents Project for Ordinary Universities(2023KQNCX043); Sailing Plan of Maoming Green Chemical Industry Research Institute(MMGCIRI-2022YFJH-Y-037); National Natural Science Foundation of China(21602035); Special Projects in Key Fields of Ordinary Universities of Guangdong Province(2020ZDZX2054)

文章分享

1. 254463S.pdf(458KB)

摘要/Abstract

报道了一种基于I₂/叔丁基过氧化氢(TBHP)促进一锅法合成α,β-不饱和酰胺的新策略. 该反应通过烯丙基苯与N,N-二烷基甲酰胺的氧化偶联实现. 值得注意的是, N,N-二烷基甲酰胺在该体系中既作为溶剂又作为反应物, 显著提升了反应的原子经济性.

关键词: I₂/叔丁基过氧化氢, 烯丙基苯, N,N-二烷基甲酰胺, α,β-不饱和酰胺

A facile one-pot strategy for the synthesis of α,β-unsaturated amides via an I₂/t-butylhydroperoxide (TBHP)- mediated oxidative system has been reported. The methodology achieves efficient construction of a series of α,β-unsaturated amides through oxidative coupling of allylbenzenes with N,N-dialkylformamides under mild conditions. Notably, N,N-dialkyl- formamides serve as both solvents and reactants in this protocol, significantly enhancing the atom economy of transformation.

Key words: I₂/t-butylhydroperoxide, allylbenzene, N,N-dialkylformamide, α,β-unsaturated amide

引用此文

苏任华, 肖朵朵, 周鹏, 龙义福, 刘卫兵. I₂/叔丁基过氧化氢促进烯丙基芳烃与二烷基甲酰胺氧化偶联合成α,β-不饱和酰胺[J]. 有机化学, 2025, 45(12): 4463-4467.

Renhua Su, Duoduo Xiao, Peng Zhou, Yifu Long, Weibing Liu. I₂/t-Butylhydroperoxide Mediated Oxidative Coupling of Allylbenze- nes with Dialkylformamides to Access α,β-Unsaturated Amides[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4463-4467.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 5

参考文献 21

[1]	(a) Harrold M. W.; Wallace R. A.; Farooqui T.; Wallace L. J.; Uretsky N.; Miller D. D. J. Med. Chem. 1989, 32, 874. pmid: 2522993
	(b) Nahm M. R.; Potnick J. R.; White P. S.; Johnson J. S. J. Am. Chem. Soc. 2006, 128, 2751. doi: 10.1021/ja056018x pmid: 2522993
	(c) Pardin C.; Pelletier J. N.; Lubell W. D.; Keillor J. W. J. Org. Chem. 2008, 73, 5766. doi: 10.1021/jo8004843 pmid: 2522993
[2]	(a) Costall B.; Hui S.-C. G.; Naylor R. J. J. Pharm. Pharmacol. 1980, 32, 594. pmid: 6106706
	(b) Jiang X. F.; Zhen Y. S. Anti-Cancer Drugs 2000, 11, 49. doi: 10.1097/00001813-200001000-00008 pmid: 6106706
	(c) Deng X. Q.; Wu D.; Wei C. X.; Quan Z. S. Med. Chem. Res. 2011, 20, 1273. doi: 10.1007/s00044-010-9470-7 pmid: 6106706
	(d) Surendran S.; Babu M.; Joseph J.; Padma U. D. Res. J. Pharm. Technol. 2020, 13, 651. pmid: 6106706
	(e) Wang Y.; Gao M.; Zhong Y.; Wu B. Polycyclic Aromat. Compd. 2023, 44, 5138. doi: 10.1080/10406638.2023.2261586 pmid: 6106706
	(f) Khan T. A.; Al Nasr I. S.; Koko W. S.; Ma J.; Eckert S.; Brehm L.; Said R. S. B.; Daoud I.; Hanachi R.; Rahali S.; van de Sande W.; Ersfeld K.; Schobert R.; Biersack B. ChemMedChem 2023, 18, e202300132. doi: 10.1002/cmdc.v18.12 pmid: 6106706
[3]	(a) Valeur E.; Bradley M. Chem. Soc. Rev. 2009, 38, 606. doi: 10.1039/b701677h pmid: 27529837
	(b) Kim Y.; Chang S. Angew. Chem., Int. Ed. 2016, 55, 218. doi: 10.1002/anie.v55.1 pmid: 27529837
	(c) Yamada K.; Karuo Y.; Tsukada Y.; Kunishima M. Chem.-Eur. J. 2016, 22, 14042. doi: 10.1002/chem.201603120 pmid: 27529837
[4]	(a) Fujihara T.; Katafuchi Y.; Iwai T.; Terao J.; Tsuji Y. J. Am. Chem. Soc. 2010, 132, 2094. doi: 10.1021/ja910038p
	(b) Kumar P. S.; Kumar G. S.; Kumar R. A.; Reddy N. V.; Rajender Reddy K. Eur. J. Org. Chem. 2013, 2013, 1218.
	(c) Priyadarshini S.; Joseph P. A.; Kantam M. L. RSC Adv. 2013, 3, 18283. doi: 10.1039/c3ra41000e
	(d) Saberi D.; Mahdudi S.; Cheraghi S.; Heydari A. J. Organomet. Chem. 2014, 772, 222.
[5]	Zhang J. R.; Liao Y. Y.; Deng J. C.; Tang Z. L.; Xu Y. L.; Xu L.; Tang R.Y. Asian J. Org. Chem. 2017, 6, 305. doi: 10.1002/ajoc.v6.3
[6]	Wang M.-M.; Sui G.-H.; Cui X.-C.; Wang H.; Qu J.-P.; Kang Y.-B. J. Org. Chem. 2019, 84, 8267. doi: 10.1021/acs.joc.9b00872
[7]	(a) Cunico R. F.; Maity B. C. Org. Lett. 2003, 5, 4947. doi: 10.1021/ol030110l
	(b) Yang T.; Lu M.; Lin Z.; Huang M.; Cai S. Org. Biomol. Chem. 2019, 17, 449. doi: 10.1039/C8OB02938E
	(c) Yu W.; Liu L.; Huang T.; Zhou X.; Chen T. Org. Lett. 2020, 22, 7123. doi: 10.1021/acs.orglett.0c02462
	(d) Lai M.; Wu Z.; Su F.; Yu Y.; Jing Y.; Kong J.; Wang Z.; Wang S.; Zhao M. Eur. J. Org. Chem. 2020, 2020, 198. doi: 10.1002/ejoc.v2020.2
	(e) Wang E.; Yang L.; He L.; Yang Q.; Wang X.; Liu Y.; Li M.; Lei Y.; Yang X. Molecules 2024, 29, 4632. doi: 10.3390/molecules29194632
[8]	(a) Escorihuela J.; Lledós A.; Ujaque G. Chem. Rev. 2023, 123, 9139. doi: 10.1021/acs.chemrev.2c00482 pmid: 37406078
	(b) Zhang S.; Findlater M. ACS Catal. 2023, 13, 8731. doi: 10.1021/acscatal.3c01221 pmid: 37406078
[9]	Yang X. H.; Wei W. T.; Li H. B.; Song R. J.; Li J. H. Chem. Commun. 2014, 50, 12867. doi: 10.1039/C4CC05051G
[10]	Lu M.; Lin Z.; Chen S.; Chen H.; Huang M.; Cai S. Org. Lett. 2019, 21, 9929. doi: 10.1021/acs.orglett.9b03870
[11]	Zhang J.; Xiao D.; Tan H.; Liu W. J. Org. Chem. 2020, 85, 3929. doi: 10.1021/acs.joc.9b03156
[12]	Zhang J.; Zhou P.; Yin A.; Zhang S.; Liu W. J. Org. Chem. 2021, 86, 8980. doi: 10.1021/acs.joc.1c00823
[13]	Xiao D.; Liu H.; Zhou P.; Zhang J.; Liu W. Chin. J. Org. Chem. 2022, 42, 1438. (in Chinese)
	(肖朵朵, 刘海灵, 周鹏, 张建涛, 刘卫兵, 有机化学, 2022, 42, 1438.) doi: 10.6023/cjoc202110005
[14]	Zhang J.; Zhu W.; Xiao D.; Zhou P.; Huang L.; Liu W. J. Org. Chem. 2024, 89, 1524. doi: 10.1021/acs.joc.3c02119
[15]	Zhou M. X.; Song Q. L. Synthesis 2014, 1853.
[16]	Zhao Q.; Miao T.; Zhang X.; Zhou W.; Wang L. Org. Biomol. Chem. 2013, 11, 1867. doi: 10.1039/c3ob27433k
[17]	Wan Y.; Alterman M.; Larhed M.; Hallberg A. J. Org. Chem. 2002, 67, 6232. doi: 10.1021/jo025965a
[18]	Perrin D. D.; Armarego W. L. F. Purification of Laboratory Chemicals, 3rd ed.; Pergamon, Oxford, 1988.
[19]	(a) Ghosh P.; Ganguly B.; Das S. Org. Biomol. Chem. 2021, 19, 2146. doi: 10.1039/D0OB02169E
	(b) Wu X.-F.; Gong J.-L.; Qi X. Org. Biomol. Chem. 2014, 12, 5807. doi: 10.1039/C4OB00276H
[20]	(a) Zhang F.; Du P.; Chen J.; Wang H.; Luo Q.; Wan X. Org. Lett. 2014, 16, 1932. doi: 10.1021/ol5004687 pmid: 25425423
	(b) Zhang J.; Jiang J.; Xu D.; Luo Q.; Wang H.; Chen J.; Li H.; Wang Y.; Wan X. Angew. Chem., Int. Ed. 2015, 54, 1231. doi: 10.1002/anie.201408874 pmid: 25425423
	(c) Ling J.; Zhang J.; Zhao Y.; Xu Y.; Wang H.; Lv Y.; Ji M.; Ma L.; Ma M.; Wan X. Org. Biomol. Chem. 2016, 14, 5310. doi: 10.1039/C6OB00873A pmid: 25425423
	(d) Wu C. S.; Liu R. X.; Ma D. Y.; Luo C. P.; Yang L. Org. Lett. 2019, 21, 6117. doi: 10.1021/acs.orglett.9b02264 pmid: 25425423
[21]	Yan H.; Yang H.; Lu L.; Liu D.; Rong G.; Mao J. Tetrahedron 2013, 69, 7258. doi: 10.1016/j.tet.2013.06.078

Entry	TBHB/equiv.	Base	Solvent	Yield^b/%
1	4.0	Na₂CO₃	DMF	48
2	4.0	CH₃COONa	DMF	56
3	4.0	t-BuOK	DMF	70
4	4.0	DBU	DMF	36
5	4.0	DMAP	DMF	67
6	4.0	Et₃N	DMF	trace
7	4.0	DABCO	DMF	71
8	4.0	—	DMF	trace
9	4.0	DABCO (2 equiv.)	DMF	70
10	4.0	DABCO (5 equiv.)	DMF	69
11^c	4.0	DABCO	DMF	0
12^d	4.0	DABCO	DMF	55
13	1.0	DABCO	DMF	33
14	2.0	DABCO	DMF	60
15	6.0	DABCO	DMF	65
16^e	4.0	DABCO	DMF	71
17^f^,^g	4.0	DABCO	DMF	75
18^g^,^h	4.0	DABCO	DMF	76
19^f^,^g	4.0	DABCO	DMSO	66
20^f^,^g	4.0	DABCO	PhCl	59
21^f^,^g	4.0	DABCO	Dioxane	63

Entry	TBHB/equiv.	Base	Solvent	Yield^b/%
1	4.0	Na₂CO₃	DMF	48
2	4.0	CH₃COONa	DMF	56
3	4.0	t-BuOK	DMF	70
4	4.0	DBU	DMF	36
5	4.0	DMAP	DMF	67
6	4.0	Et₃N	DMF	trace
7	4.0	DABCO	DMF	71
8	4.0	—	DMF	trace
9	4.0	DABCO (2 equiv.)	DMF	70
10	4.0	DABCO (5 equiv.)	DMF	69
11^c	4.0	DABCO	DMF	0
12^d	4.0	DABCO	DMF	55
13	1.0	DABCO	DMF	33
14	2.0	DABCO	DMF	60
15	6.0	DABCO	DMF	65
16^e	4.0	DABCO	DMF	71
17^f^,^g	4.0	DABCO	DMF	75
18^g^,^h	4.0	DABCO	DMF	76
19^f^,^g	4.0	DABCO	DMSO	66
20^f^,^g	4.0	DABCO	PhCl	59
21^f^,^g	4.0	DABCO	Dioxane	63

I₂/叔丁基过氧化氢促进烯丙基芳烃与二烷基甲酰胺氧化偶联合成α,β-不饱和酰胺

I₂/t-Butylhydroperoxide Mediated Oxidative Coupling of Allylbenze- nes with Dialkylformamides to Access α,β-Unsaturated Amides

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 5

参考文献 21

相关文章 1

编辑推荐

相关统计

本文评价