Synthesis of 3,5-Disubstituted Isoxazolines Mediated by Catalytic Alkyl Iodide†

doi:10.7503/cjcu20141016

Abstract

Abstract:

A new method for the preparation of 3,5-disubstituted isoxazolines using a catalytic amount of 1-iodopropane was developed and the optimization of the reaction conditions was obtained. The possible mechanism for the cycloaddition was suggested as followed: 1-iodopropane was first oxidized by oxone into the hypervalent iodine intermediate, then it decomposed at once to form hypoiodous acid, the in situ generated hypoiodous acid reacted with oxime and alkene, and after an elimination of HI, the reaction provided the desired isoxazoline. The new method has some advantages such as mild reaction conditions, simple procedure and good yields.

Key words: Isoxazoline, Hypoiodous acid, Alkyl iodide, Catalytic oxidation

CLC Number:

O621.3

TrendMD:

FANG Yingguo, ZHU Min. Synthesis of 3,5-Disubstituted Isoxazolines Mediated by Catalytic Alkyl Iodide^†[J]. Chem. J. Chinese Universities, 2015, 36(4): 660.

Figures/Tables 5

References 39

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Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃
3a	72—73(74—75^[34])	3g	60—62(59—61^[31])
3b	75—76(72—76^[34])	3h	96—97(97^[16])
3c	128—129(129.8—130.3^[33])	3i	103—105(103—104^[16])
3d	67—69(67.5—68.2^[4])	3j	88—90(91—92^[37])
3e	39—41(40—42^[35])	3m	136—138(138—139^[13])
3f	69—71(71—72.5^[36])

Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃
3a	72—73(74—75^[34])	3g	60—62(59—61^[31])
3b	75—76(72—76^[34])	3h	96—97(97^[16])
3c	128—129(129.8—130.3^[33])	3i	103—105(103—104^[16])
3d	67—69(67.5—68.2^[4])	3j	88—90(91—92^[37])
3e	39—41(40—42^[35])	3m	136—138(138—139^[13])
3f	69—71(71—72.5^[36])

Entry	n(Styrene):n(RI)^a:n(Oxidant)^b	Solvent	Time/h	Yield^c(%)
1	1.1:0.2:1.3	CH₃OH	12	25
2	1.1:0.2:1.3	CH₃CH₂OH	12	Trace
3	1.1:0.2:1.3	CH₂Cl₂	12	8
4	1.1:0.2:1.3	THF	12	Trace
5	1.1:0.2:1.3	H₂O	12	65
6	1.1:0.2:1.3	DMF	12	5
7	1.1:0.2:1.3	CH₃CN	12	6
8	1.1:0.2:1.3	CF₃CH₂OH	12	87
9	1.1:0:1.3	CF₃CH₂OH	12	0
10	1.5:0.2:1.3	CF₃CH₂OH	12	89
11	1.7:0.2:1.3	CF₃CH₂OH	12	93
12	2.0:0.2:1.3	CF₃CH₂OH	12	92
13	1.7:0.2:1.1	CF₃CH₂OH	12	65
14	1.7:0.2:1.5	CF₃CH₂OH	12	92
15	1.7:0.2:1.7	CF₃CH₂OH	12	93
16	1.7:0.2:2.0	CF₃CH₂OH	12	92
17	1.7:0.1:1.3	CF₃CH₂OH	12	83
18	1.7:0.3:1.3	CF₃CH₂OH	12	95
19	1.7:0.4:1.3	CF₃CH₂OH	12	94
20	1.7:0.2:1.3	CF₃CH₂OH	12	78
21	1.7:0.2:1.3	CF₃CH₂OH	12	93
22	1.7:0.2:1.3	CF₃CH₂OH	12	92
23	1.7:0.2:1.3	CF₃CH₂OH	12	71
24	1.7:0.2:1.3	CF₃CH₂OH	12	77
25	1.7:0.2:1.3	CF₃CH₂OH	3	43
26	1.7:0.2:1.3	CF₃CH₂OH	4	49
27	1.7:0.2:1.3	CF₃CH₂OH	6	56
28	1.7:0.2:1.3	CF₃CH₂OH	24	92

Entry	n(Styrene):n(RI)^a:n(Oxidant)^b	Solvent	Time/h	Yield^c(%)
1	1.1:0.2:1.3	CH₃OH	12	25
2	1.1:0.2:1.3	CH₃CH₂OH	12	Trace
3	1.1:0.2:1.3	CH₂Cl₂	12	8
4	1.1:0.2:1.3	THF	12	Trace
5	1.1:0.2:1.3	H₂O	12	65
6	1.1:0.2:1.3	DMF	12	5
7	1.1:0.2:1.3	CH₃CN	12	6
8	1.1:0.2:1.3	CF₃CH₂OH	12	87
9	1.1:0:1.3	CF₃CH₂OH	12	0
10	1.5:0.2:1.3	CF₃CH₂OH	12	89
11	1.7:0.2:1.3	CF₃CH₂OH	12	93
12	2.0:0.2:1.3	CF₃CH₂OH	12	92
13	1.7:0.2:1.1	CF₃CH₂OH	12	65
14	1.7:0.2:1.5	CF₃CH₂OH	12	92
15	1.7:0.2:1.7	CF₃CH₂OH	12	93
16	1.7:0.2:2.0	CF₃CH₂OH	12	92
17	1.7:0.1:1.3	CF₃CH₂OH	12	83
18	1.7:0.3:1.3	CF₃CH₂OH	12	95
19	1.7:0.4:1.3	CF₃CH₂OH	12	94
20	1.7:0.2:1.3	CF₃CH₂OH	12	78
21	1.7:0.2:1.3	CF₃CH₂OH	12	93
22	1.7:0.2:1.3	CF₃CH₂OH	12	92
23	1.7:0.2:1.3	CF₃CH₂OH	12	71
24	1.7:0.2:1.3	CF₃CH₂OH	12	77
25	1.7:0.2:1.3	CF₃CH₂OH	3	43
26	1.7:0.2:1.3	CF₃CH₂OH	4	49
27	1.7:0.2:1.3	CF₃CH₂OH	6	56
28	1.7:0.2:1.3	CF₃CH₂OH	24	92

Compd.	Time/h	Yield^a(%)	Compd.	Time/h	Yield^a(%)
3a	12	93(88)^b	3h	12	80(76)^b
3b	12	60	3i	12	73
3c	12	81(92)^b	3j	12	76
3d	24	79(81)^b	3k	24	62
3e	24	65	3l	24	61
3f	12	85	3m	24	48(8)^b
3g	24	70