Silver-Catalyzed Synthesis of CF3-Substituted 2-Imidazolines

doi:10.6023/cjoc202111009

Abstract

The silver salt catalyzed [3+2] cycloaddition reaction of trifluoromethylated N-acylhydrazones and ethyl isocyanoacetate was investigated. The reaction proceeds quickly to produce a series of trifluoromethylated 2-imidazoline compounds in high yields with excellent stereoselectivity, which provides a novel and efficient method for the synthesis of trifluoromethylated 2-imidazoline compounds.

Key words: trifluoromethylated N-acylhydrazone, ethyl isocyanoacetate, [3+2] cycloaddition, 2-imidazoline

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Ming Yang, Danfeng Huang, Kehu Wang, Tongyu Han, Pengfei Zhao, Feng Wang, Junjiao Wang, Yingpeng Su, Yulai Hu. Silver-Catalyzed Synthesis of CF₃-Substituted 2-Imidazolines[J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1509-1519.

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Fig. & Tab. 6

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Entry	Mole ratio of 1a/2a/catalyst/base	Catalyst	Base	Solvent	Time/h	Isolated yield/%
1	1∶2∶0∶2	—	DBU	CHCl₃	72	35
2	1∶2∶0.2∶0	CuI	—	CHCl₃	12	0
3	1∶2∶0.2∶0.2	CuI	DBU	CHCl₃	12	80
4	1∶2.5∶0.2∶0.2	CuI	DBU	CHCl₃	12	70
5	1∶1.5∶0.2∶0.2	CuI	DBU	CHCl₃	12	74
6	1∶2∶0.2∶0.2	CuI	DBU	CH₂Cl₂	12	50
7	1∶2∶0.2∶0.2	CuI	DBU	DCE	12	76
8	1∶2∶0.2∶0.2	CuI	DBU	EtOH	12	45
9	1∶2∶0.2∶0.2	CuI	DBU	CH₃CN	12	40
10	1∶2∶0.2∶0.2	CuI	DBU	Toluene	12	73
11	1∶2∶0.2∶0.2	CuI	DBU	1,4-Dioxane	12	76
12	1∶2∶0.2∶0.2	CuI	DBU	THF	12	82
13	1∶2∶0.2∶0.2	CuI	DBU	THF	7	85
14	1∶2∶0.2∶0.2	CuI	Et₃N	THF	72	0
15	1∶2∶0.2∶0.2	CuI	DABCO	THF	72	0
16	1∶2∶0.2∶0.2	CuI	K₂CO₃	THF	72	20
17	1∶2∶0.2∶0.2	CuI	Na₂CO₃	THF	72	25
18	1∶2∶0.2∶0.2	CuI	Cs₂CO₃	THF	72	13
Entry	Mole ratio of 1a/2a/catalyst/base	Catalyst	Base	Solvent	Time/h	Isolated yield/%
19	1∶2∶0.2∶0.2	Ag₂CO₃	DBU	THF	1	88
20	1∶2∶0.2∶0.2	AgOAc	DBU	THF	40 min	90
21	1∶2∶0.2∶0.2	AgOTf	DBU	THF	2	88
22	1∶2∶0.2∶0.2	Ag₂O	DBU	THF	1	86
23	1∶2∶0.2∶0.2	AgNO₃	DBU	THF	3	61
24	1∶2∶0.2∶0	AgOAc	—	THF	40 min	90
25	1∶2∶0.1∶0	AgOAc	—	THF	40 min	26

Entry	Mole ratio of 1a/2a/catalyst/base	Catalyst	Base	Solvent	Time/h	Isolated yield/%
1	1∶2∶0∶2	—	DBU	CHCl₃	72	35
2	1∶2∶0.2∶0	CuI	—	CHCl₃	12	0
3	1∶2∶0.2∶0.2	CuI	DBU	CHCl₃	12	80
4	1∶2.5∶0.2∶0.2	CuI	DBU	CHCl₃	12	70
5	1∶1.5∶0.2∶0.2	CuI	DBU	CHCl₃	12	74
6	1∶2∶0.2∶0.2	CuI	DBU	CH₂Cl₂	12	50
7	1∶2∶0.2∶0.2	CuI	DBU	DCE	12	76
8	1∶2∶0.2∶0.2	CuI	DBU	EtOH	12	45
9	1∶2∶0.2∶0.2	CuI	DBU	CH₃CN	12	40
10	1∶2∶0.2∶0.2	CuI	DBU	Toluene	12	73
11	1∶2∶0.2∶0.2	CuI	DBU	1,4-Dioxane	12	76
12	1∶2∶0.2∶0.2	CuI	DBU	THF	12	82
13	1∶2∶0.2∶0.2	CuI	DBU	THF	7	85
14	1∶2∶0.2∶0.2	CuI	Et₃N	THF	72	0
15	1∶2∶0.2∶0.2	CuI	DABCO	THF	72	0
16	1∶2∶0.2∶0.2	CuI	K₂CO₃	THF	72	20
17	1∶2∶0.2∶0.2	CuI	Na₂CO₃	THF	72	25
18	1∶2∶0.2∶0.2	CuI	Cs₂CO₃	THF	72	13
Entry	Mole ratio of 1a/2a/catalyst/base	Catalyst	Base	Solvent	Time/h	Isolated yield/%
19	1∶2∶0.2∶0.2	Ag₂CO₃	DBU	THF	1	88
20	1∶2∶0.2∶0.2	AgOAc	DBU	THF	40 min	90
21	1∶2∶0.2∶0.2	AgOTf	DBU	THF	2	88
22	1∶2∶0.2∶0.2	Ag₂O	DBU	THF	1	86
23	1∶2∶0.2∶0.2	AgNO₃	DBU	THF	3	61
24	1∶2∶0.2∶0	AgOAc	—	THF	40 min	90
25	1∶2∶0.1∶0	AgOAc	—	THF	40 min	26

银催化下三氟甲基取代的2-咪唑啉化合物的合成

Silver-Catalyzed Synthesis of CF₃-Substituted 2-Imidazolines

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[2]	Zhou Baoyue, Zhang Jin, Li Xiangnan, She Mengyao, Zhang Jing, Li Jianli, Shi Zhen. Progress in the Synthesis and Applications of 2-Imidazolines [J]. Chin. J. Org. Chem., 2013, 33(03): 423-435.