High-Selective One-Pot Synthesis of Spirocyclopropane Pyrazolones Promoted by 4-Dimethylaminopyridine

doi:10.6023/cjoc201904028

Abstract

A 4-dimethylaminopyridine (DMAP)-promoted high stereoselectivity method for the synthesis of polysubstituted spiropropane pyrazolone was developed. A series of target compounds were synthesized from using pyrazolone, aromatic aldehyde and bromoacetate as raw materials, and DMAP as a base with high yield via three-component one-pot reaction. This reaction has the advantages of simple operation, high yield and good diastereotopic selectivity. In addition, this synthetic method is of great value for the study of spiropropane.

Key words: one-pot synthesis, multicomponent reactions, spirocyclopropane, pyrazolones, 4-dimethylaminopyridine (DMAP)

Cite this article

Liang Jie, Ma Huifang, Ablajan Keyume. High-Selective One-Pot Synthesis of Spirocyclopropane Pyrazolones Promoted by 4-Dimethylaminopyridine[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3169-3175.

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Entry	Base	Solvent	Temp./℃	Yield^b/%	trans^c/cis
1	No base	CH₃CN	81	NR	NR
2	NaOH	CH₃CN	81	41	45:55
3	Cs₂CO₃	CH₃CN	81	48	48:52
4	Pyridine	CH₃CN	81	82^c	72:28
5	TEBA	CH₃CN	81	56	80:20
6	CTAB	CH₃CN	81	60	85:15
7	DABCO	CH₃CN	81	70	72:28
8	DMAP	CH₃CN	81	86	94:6
9	DMAP	CH₂Cl₂	81	65	40:60
10	DMAP	H₂O	100	Trace	NR
11	DMAP	CH₃CO₂Et	81	78	88:12
12	DMAP	CH₃CN	81	86^d	94:6
13	DMAP	CH₃CN	25	36	46:54
14	DMAP	CH₃CN	60	68	79:21
15	DMAP	CH₃CN	81	50^e	90:10


Entry	Base	Solvent	Temp./℃	Yield^b/%	trans^c/cis
1	No base	CH₃CN	81	NR	NR
2	NaOH	CH₃CN	81	41	45:55
3	Cs₂CO₃	CH₃CN	81	48	48:52
4	Pyridine	CH₃CN	81	82^c	72:28
5	TEBA	CH₃CN	81	56	80:20
6	CTAB	CH₃CN	81	60	85:15
7	DABCO	CH₃CN	81	70	72:28
8	DMAP	CH₃CN	81	86	94:6
9	DMAP	CH₂Cl₂	81	65	40:60
10	DMAP	H₂O	100	Trace	NR
11	DMAP	CH₃CO₂Et	81	78	88:12
12	DMAP	CH₃CN	81	86^d	94:6
13	DMAP	CH₃CN	25	36	46:54
14	DMAP	CH₃CN	60	68	79:21
15	DMAP	CH₃CN	81	50^e	90:10


Entry	R¹	R²	R³	4	Yield^b/%	trans/cis^c
1	Ph	4-ClC₆H₄	Me	4a	62	6:1
2	Ph	4-BrC₆H₄	Me	4b	67	8:1
3	Ph	2-O₂NC₆H₄	Me	4c	84	11:1
4	Ph	2-ClC₆H₄	Me	4d	85	12:1
5	Ph	2, 4-Cl₂C₆H₄	Me	4e	79	10:1
6	4-CH₃C₆H₄	4-ClC₆H₄	Me	4f	62	15:1
7	4-CH₃C₆H₄	4-BrC₆H₄	Me	4g	65	11:1
8	4-CH₃C₆H₄	2-O₂NC₆H₄	Me	4h	86	18:1
9	4-CH₃C₆H₄	2-ClC₆H₄	Me	4i	86	17:1
10	4-CH₃C₆H₄	2, 4-Cl₂C₆H₄	Me	4j	80	15:1
11	4-CH₃C₆H₄	Ph	Me	4k	65	6:1
12	4-ClC₆H₄	4-ClC₆H₄	Me	4l	62	9:1
13	4-ClC₆H₄	4-BrC₆H₄	Me	4m	66	8:1
14	4-ClC₆H₄	2-O₂NC₆H₄	Me	4n	58	> 25:1
15	4-ClC₆H₄	2, 4-Cl₂C₆H₄	Me	4o	82	15:1
16	2-ClC₆H₄	4-ClC₆H₄	Me	4p	77	11:1
17	2-ClC₆H₄	4-BrC₆H₄	Me	4q	78	12:1
18	2-ClC₆H₄	2-O₂NC₆H₄	Me	4r	83	18:1
19	2-ClC₆H₄	2, 4-Cl₂C₆H₄	Me	4s	80	13:1
20	Ph	2, 4-Cl₂C₆H₄	C(Me)₃	4t	89	> 25:1
21	4-CH₃C₆H₄	2-O₂NC₆H₄	C(Me)₃	4u	87	> 25:1
22	2-ClC₆H₄	2-O₂NC₆H₄	C(Me)₃	4v	87	> 25:1
23	4-ClC₆H₄	2, 4-Cl₂C₆H₄	C(Me)₃	4w	85	> 25:1


Entry	R¹	R²	R³	4	Yield^b/%	trans/cis^c
1	Ph	4-ClC₆H₄	Me	4a	62	6:1
2	Ph	4-BrC₆H₄	Me	4b	67	8:1
3	Ph	2-O₂NC₆H₄	Me	4c	84	11:1
4	Ph	2-ClC₆H₄	Me	4d	85	12:1
5	Ph	2, 4-Cl₂C₆H₄	Me	4e	79	10:1
6	4-CH₃C₆H₄	4-ClC₆H₄	Me	4f	62	15:1
7	4-CH₃C₆H₄	4-BrC₆H₄	Me	4g	65	11:1
8	4-CH₃C₆H₄	2-O₂NC₆H₄	Me	4h	86	18:1
9	4-CH₃C₆H₄	2-ClC₆H₄	Me	4i	86	17:1
10	4-CH₃C₆H₄	2, 4-Cl₂C₆H₄	Me	4j	80	15:1
11	4-CH₃C₆H₄	Ph	Me	4k	65	6:1
12	4-ClC₆H₄	4-ClC₆H₄	Me	4l	62	9:1
13	4-ClC₆H₄	4-BrC₆H₄	Me	4m	66	8:1
14	4-ClC₆H₄	2-O₂NC₆H₄	Me	4n	58	> 25:1
15	4-ClC₆H₄	2, 4-Cl₂C₆H₄	Me	4o	82	15:1
16	2-ClC₆H₄	4-ClC₆H₄	Me	4p	77	11:1
17	2-ClC₆H₄	4-BrC₆H₄	Me	4q	78	12:1
18	2-ClC₆H₄	2-O₂NC₆H₄	Me	4r	83	18:1
19	2-ClC₆H₄	2, 4-Cl₂C₆H₄	Me	4s	80	13:1
20	Ph	2, 4-Cl₂C₆H₄	C(Me)₃	4t	89	> 25:1
21	4-CH₃C₆H₄	2-O₂NC₆H₄	C(Me)₃	4u	87	> 25:1
22	2-ClC₆H₄	2-O₂NC₆H₄	C(Me)₃	4v	87	> 25:1
23	4-ClC₆H₄	2, 4-Cl₂C₆H₄	C(Me)₃	4w	85	> 25:1

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