Ligand-Free Iron-Catalyzed Intramolecular Amination of C(sp3)—H Bond for the Synthesis of Imidazolinones

doi:10.6023/cjoc202104054

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (10): 4083-4087.DOI: 10.6023/cjoc202104054 Previous Articles Next Articles

Special Issue: 南开大学化学学科创立100周年；热点论文虚拟合集

NOTES

无配体参与的铁催化分子内C(sp³)—H键胺化合成咪唑啉酮

邬林洋, 钟大猷, 刘文博^*()

武汉大学化学与分子科学学院索维奇国际分子科学研究中心有机硅化合物及材料教育部工程研究中心武汉 430072

收稿日期:2021-04-26 修回日期:2021-05-09 发布日期:2021-05-14
通讯作者: 刘文博
基金资助:
国家自然科学基金(21971198); 国家自然科学基金(21772148)

Ligand-Free Iron-Catalyzed Intramolecular Amination of C(sp³)—H Bond for the Synthesis of Imidazolinones

Linyang Wu, Dayou Zhong, Wenbo Liu()

Sauvage Center for Molecular Sciences, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072

Received:2021-04-26 Revised:2021-05-09 Published:2021-05-14
Contact: Wenbo Liu
Supported by:
National Natural Science Foundation of China(21971198); National Natural Science Foundation of China(21772148)

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Abstract

Transition-metal-nitrenoids intramolecular C—H insertion is one of the most effective methods to synthesize nitrogen-containing heterocycles. Using 2-azido-N,N-dibenzylacetamides as substrates, an iron-catalyzed intramolecular C(sp³)—H bond amination reaction under ligand-free and external oxidant-free conditions has been developed. A series of imidazolinones were synthesized in moderate to good yields.

Key words: iron catalysis, nitrene insertion, imidazolinone, synthesis of N-containing heterocycles

Cite this article

Linyang Wu, Dayou Zhong, Wenbo Liu. Ligand-Free Iron-Catalyzed Intramolecular Amination of C(sp³)—H Bond for the Synthesis of Imidazolinones[J]. Chinese Journal of Organic Chemistry, 2021, 41(10): 4083-4087.

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Entry	FeX₂	Solvent	T/℃	Yield^b/% of 2
1	FeCl₂	DCE	85	58
2	FeBr₂	DCE	85	59 (54)^c
3	Fe(ClO₄)₂	DCE	85	59
4	Fe(OTf)₂	DCE	85	34
5	—	DCE	85	—
6	FeBr₂^d	DCE	85	—
7	FeBr₂	DCE	65	61 (59)^c
8	FeBr₂	DCE	45	21
9	FeBr₂	DCE	25	8
10	FeBr₂	oluene	65	57
11	FeBr₂	MeCN	65	22
12	FeBr₂	MTBE	65	24
13	FeBr₂	THF	65	13

Entry	FeX₂	Solvent	T/℃	Yield^b/% of 2
1	FeCl₂	DCE	85	58
2	FeBr₂	DCE	85	59 (54)^c
3	Fe(ClO₄)₂	DCE	85	59
4	Fe(OTf)₂	DCE	85	34
5	—	DCE	85	—
6	FeBr₂^d	DCE	85	—
7	FeBr₂	DCE	65	61 (59)^c
8	FeBr₂	DCE	45	21
9	FeBr₂	DCE	25	8
10	FeBr₂	oluene	65	57
11	FeBr₂	MeCN	65	22
12	FeBr₂	MTBE	65	24
13	FeBr₂	THF	65	13

Entry	R¹	R²	R³	Time/h	Yield^b/% of 2
1	Ph	Ph	H	1	59 (2a)
2	4-MeC₆H₄	4-MeC₆H₄	H	6	52 (2b)
3	4-^tBuC₆H₄	4-^tBuC₆H₄	H	6	63 (2c)
4	4-FC₆H₄	4-FC₆H₄	H	5	47 (2d)
5	4-ClC₆H₄	4-ClC₆H₄	H	5	60 (2e)
6	4-BrC₆H₄	4-BrC₆H₄	H	5	60 (2f)
7	4-MeOC₆H₄	4-MeOC₆H₄	H	4	55 (2g)
8	4-CF₃C₆H₄	4-CF₃C₆H₄	H	2	72 (2h)
9	2-Thienyl	2-Thienyl	H	1	75 (2i)
10^c	4-MeOC₆H₄	4-O₂NC₆H₄	H	2	39 (2j)
10^c	4-O₂NC₆H₄	4-MeOC₆H₄	H	2	21 (2j')
11	Ph	Ph	Me	6	NR

Entry	R¹	R²	R³	Time/h	Yield^b/% of 2
1	Ph	Ph	H	1	59 (2a)
2	4-MeC₆H₄	4-MeC₆H₄	H	6	52 (2b)
3	4-^tBuC₆H₄	4-^tBuC₆H₄	H	6	63 (2c)
4	4-FC₆H₄	4-FC₆H₄	H	5	47 (2d)
5	4-ClC₆H₄	4-ClC₆H₄	H	5	60 (2e)
6	4-BrC₆H₄	4-BrC₆H₄	H	5	60 (2f)
7	4-MeOC₆H₄	4-MeOC₆H₄	H	4	55 (2g)
8	4-CF₃C₆H₄	4-CF₃C₆H₄	H	2	72 (2h)
9	2-Thienyl	2-Thienyl	H	1	75 (2i)
10^c	4-MeOC₆H₄	4-O₂NC₆H₄	H	2	39 (2j)
10^c	4-O₂NC₆H₄	4-MeOC₆H₄	H	2	21 (2j')
11	Ph	Ph	Me	6	NR

无配体参与的铁催化分子内C(sp³)—H键胺化合成咪唑啉酮

Ligand-Free Iron-Catalyzed Intramolecular Amination of C(sp³)—H Bond for the Synthesis of Imidazolinones

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无配体参与的铁催化分子内C(sp3)—H键胺化合成咪唑啉酮