A Highly Efficient Co-catalytic Beckmann Rearrangement Reaction†

doi:10.7503/cjcu20170560

Abstract

Abstract:

Beckmann rearrangement reaction represents one of the most significant reactions in organic synthesis, and plays a very important role in the field of synthetic chemistry. The traditional Beckmann rearrangement reactions generally require high temperature and strong acids, and suffer from harsh conditions and serious environmental pollution. In this work, based on the efficient and commercial available cobalt tetrafluoroborate hexahydrate, the catalyst systems capable of highly efficient catalytic Beckmann rearrangement of ketoxime derivatives were developed, providing the amides with broad functional-group compatibility and high yields(up to 97%). With the active Co-catalyst in hands, the catalytic system also successfully conducted the transformantion on a 10 gram-grade scale, gaving the desirable product in 71% yield. Moreover, the Co-catalyzed Beckmann rearrangement reaction was extended to a one-pot protocol using ketone and hydroxylamine hydrochloride as reactive materials, offering the yield of products up to 94%. The novel system proceeded with additives and solvent free, and showed high atom-economy and good functional-group tolerance.

Key words: Beckmann rearrangement, Cobalt catalyst, Ketone, Ketoxime, Amide

CLC Number:

O626.4

TrendMD:

YAO Wubing,YU Jiangjiang,HUANG Xiangyun,ZHANG Bin. A Highly Efficient Co-catalytic Beckmann Rearrangement Reaction^†[J]. Chem. J. Chinese Universities, 2018, 39(5): 926.

Figures/Tables 10

References 49

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Compd.	Appearance	Yield(%)	m. p./℃(Ref.)	Compd.	Appearance	Yield(%)	m. p./℃(Ref.)
1a	White solid	60	143—146(140—144^[42])	2a	White solid	93	136—140(134—135^[45])
1b	White solid	84	131—134(133—135^[41])	2b	Yellow solid	77	137—154(141—145^[41])
1c	White solid	80	131—133(129—130^[41])	2c	White solid	95	199—203(204—205^[41])
1d	Yellow solid	80	189—192(193—194^[43])	2e	White solid	86	115—119(113—115^[46])
1e	White solid	78	54—60(55—60^[42])	2f	White solid	87	148—150(148—151^[47])
1f	White solid	72	87—90(85—87^[42])	2g	White solid	91	131—137(128—130^[47])
1g	White solid	75	85—88(86—87^[42])	2h	White solid	73	168—176(176—178^[47])
1h	White solid	82	97—99(96—98^[42])	2i	White solid	82	102—106(104—107^[48])
1i	White solid	77	51—54(56—58^[42])	2j	White solid	46	67—70(68—71^[48])
1j	White solid	78	87—90(88—92^[44])	4j	Colorles soil	63

Compd.	Appearance	Yield(%)	m. p./℃(Ref.)	Compd.	Appearance	Yield(%)	m. p./℃(Ref.)
1a	White solid	60	143—146(140—144^[42])	2a	White solid	93	136—140(134—135^[45])
1b	White solid	84	131—134(133—135^[41])	2b	Yellow solid	77	137—154(141—145^[41])
1c	White solid	80	131—133(129—130^[41])	2c	White solid	95	199—203(204—205^[41])
1d	Yellow solid	80	189—192(193—194^[43])	2e	White solid	86	115—119(113—115^[46])
1e	White solid	78	54—60(55—60^[42])	2f	White solid	87	148—150(148—151^[47])
1f	White solid	72	87—90(85—87^[42])	2g	White solid	91	131—137(128—130^[47])
1g	White solid	75	85—88(86—87^[42])	2h	White solid	73	168—176(176—178^[47])
1h	White solid	82	97—99(96—98^[42])	2i	White solid	82	102—106(104—107^[48])
1i	White solid	77	51—54(56—58^[42])	2j	White solid	46	67—70(68—71^[48])
1j	White solid	78	87—90(88—92^[44])	4j	Colorles soil	63

Entry	Co catalyst	n(Co catalyst)/mmol	Solvent	t/h	T/℃	Yield(%)
1	CoSO₄	0.1	MeCN	6	100	0
2	Co(OAc)₂	0.1	MeCN	6	100	0
3	CoCl₂	0.1	MeCN	6	100	57
4			MeCN	6	100	0
5	Co(BF₄)₂·6H₂O	0.1	MeCN	6	100	97
6	Co(BF₄)₂·6H₂O	0.1	MeCN	1	100	90
7	Co(BF₄)₂·6H₂O	0.1	MeCN	3	100	97
8	Co(BF₄)₂·6H₂O	0.025	MeCN	3	100	78
9	Co(BF₄)₂·6H₂O	0.05	MeCN	3	100	95(93)
10	Co(BF₄)₂·6H₂O	0.05	THF	3	100	0
11	Co(BF₄)₂·6H₂O	0.05	DMSO	3	100	0
12	Co(BF₄)₂·6H₂O	0.05	MeCN	3	60	37
13	Co(BF₄)₂·6H₂O	0.05	MeCN	3	80	70

Entry	Co catalyst	n(Co catalyst)/mmol	Solvent	t/h	T/℃	Yield(%)
1	CoSO₄	0.1	MeCN	6	100	0
2	Co(OAc)₂	0.1	MeCN	6	100	0
3	CoCl₂	0.1	MeCN	6	100	57
4			MeCN	6	100	0
5	Co(BF₄)₂·6H₂O	0.1	MeCN	6	100	97
6	Co(BF₄)₂·6H₂O	0.1	MeCN	1	100	90
7	Co(BF₄)₂·6H₂O	0.1	MeCN	3	100	97
8	Co(BF₄)₂·6H₂O	0.025	MeCN	3	100	78
9	Co(BF₄)₂·6H₂O	0.05	MeCN	3	100	95(93)
10	Co(BF₄)₂·6H₂O	0.05	THF	3	100	0
11	Co(BF₄)₂·6H₂O	0.05	DMSO	3	100	0
12	Co(BF₄)₂·6H₂O	0.05	MeCN	3	60	37
13	Co(BF₄)₂·6H₂O	0.05	MeCN	3	80	70

Entry	Substrate	Product	Entry	Substrate	Product
1			6
	1a	2a, yield 93%		1f	2f, yield 87%
2			7
	1b	2b, yield 77%		1g	2g, yield 91%
3			8
	1c	2c, yield 95%		1h	2h, yield 73%
4			9
	1d	2d, yield 0		1i	2i, yield 82%
5			10
	1e	2e, yield 86%		1j	2j, yield 61%^b