Study of the Halide Salt Catalyzed [3＋2] Cycloaddition of α,β-Epoxy Carboxylate with Isocyanate

doi:10.6023/cjoc202305018

Abstract

The [3＋2] cycloaddition reaction of α,β-epoxy carboxylate and isocyanate was investigated. By employing magnesium bromide as a catalyst, efficient synthesis of chiral oxazolidin-2-ones was achieved through aforementioned [3＋2] cycloaddition reaction. The reaction exhibited good substrate adaptability. For reactions involving chiral epoxide compounds, the product enantiomeric excess remains good. Furthermore, under basic conditions, taxol C-13 side chain ((2R,3S)-methyl 3-benzamido-2-hydroxy-3-phenylpropanoate) was synthesized via ring-opening reaction of the chiral oxazolidin-2-ones product with an optical purity of up to 97% ee.

Key words: asymmetric synthesis, [3＋2] cycloaddition, oxazolidin-2-one, taxol side chain

Cite this article

Huakun Wang, Xiaolong Ren, Yining Xuan. Study of the Halide Salt Catalyzed [3＋2] Cycloaddition of α,β-Epoxy Carboxylate with Isocyanate[J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 251-258.

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Entry	Cat. (x/equiv.)	Solvent	Temp./℃	Time/h	Total yield^b/%
1	NaI (0.5)	THF	25	8	29
2	KI (0.5)	THF	25	8	4
3	CuI (0.5)	THF	25	8	Trace
4	TBAB (0.5)	THF	25	8	6
5	CuBr (0.5)	THF	25	8	25
6	CaBr₂ (0.5)	THF	25	8	3
7	AlBr₃ (0.5)	THF	25	8	5
8	LiBr (0.5)	THF	25	8	42
9	NaBr (0.5)	THF	25	8	Trace
10	KBr (0.5)	THF	25	8	Trace
11	MgBr₂ (0.5)	THF	25	8	54
12	MgI₂ (0.5)	THF	25	8	32
13	MgBr₂ (0.2)	THF	25	8	77
14	MgBr₂ (0.2)	CH₂Cl₂	25	8	55
15	MgBr₂ (0.2)	CH₂ClCH₂Cl	25	8	63
16	MgBr₂ (0.2)	CH₃CN	25	8	70
17	MgBr₂ (0.2)	Et₂O	25	8	30
18	MgBr₂ (0.2)	Toluene	25	8	60
19	MgBr₂ (0.2)	DMF	25	8	72
20	MgBr₂ (0.2)	THF	80	4	86
21	MgBr₂ (0.1)	THF	80	4	48
22	MgI₂ (0.5)	THF	80	4	52
23	MgI₂ (0.2)	THF	80	4	61
24	LiBr (0.2)	THF	25	8	2
25	3-羟基-N-辛基吡啶鎓碘化物^c (0.1)	THF	80	10	9
26	TBAI (0.2) 抗坏血酸(0.1)	THF	80	8	16

Entry	Cat. (x/equiv.)	Solvent	Temp./℃	Time/h	Total yield^b/%
1	NaI (0.5)	THF	25	8	29
2	KI (0.5)	THF	25	8	4
3	CuI (0.5)	THF	25	8	Trace
4	TBAB (0.5)	THF	25	8	6
5	CuBr (0.5)	THF	25	8	25
6	CaBr₂ (0.5)	THF	25	8	3
7	AlBr₃ (0.5)	THF	25	8	5
8	LiBr (0.5)	THF	25	8	42
9	NaBr (0.5)	THF	25	8	Trace
10	KBr (0.5)	THF	25	8	Trace
11	MgBr₂ (0.5)	THF	25	8	54
12	MgI₂ (0.5)	THF	25	8	32
13	MgBr₂ (0.2)	THF	25	8	77
14	MgBr₂ (0.2)	CH₂Cl₂	25	8	55
15	MgBr₂ (0.2)	CH₂ClCH₂Cl	25	8	63
16	MgBr₂ (0.2)	CH₃CN	25	8	70
17	MgBr₂ (0.2)	Et₂O	25	8	30
18	MgBr₂ (0.2)	Toluene	25	8	60
19	MgBr₂ (0.2)	DMF	25	8	72
20	MgBr₂ (0.2)	THF	80	4	86
21	MgBr₂ (0.1)	THF	80	4	48
22	MgI₂ (0.5)	THF	80	4	52
23	MgI₂ (0.2)	THF	80	4	61
24	LiBr (0.2)	THF	25	8	2
25	3-羟基-N-辛基吡啶鎓碘化物^c (0.1)	THF	80	10	9
26	TBAI (0.2) 抗坏血酸(0.1)	THF	80	8	16

Entry	R¹	ee^b/%	R² (3)	Main product	Total yield^c/%	4∶5^d	ee^e/%
1	C₆H₅ (2a)	98	C₆H₅CO (3a)	4a	86	92∶8	97
2	2-ClC₆H₄ (2b)	97	C₆H₅CO (3a)	4b	65	82∶18	93
3	3-ClC₆H₄ (2c)	95	C₆H₅CO (3a)	4c	90	80∶20	93
4	4-ClC₆H₄ (2d)	99	C₆H₅CO (3a)	4d	94	87∶13	93
5	4-BrC₆H₄ (2e)	96	C₆H₅CO (3a)	4e	94	91∶9	95
6	4-NCC₆H₄ (2f)	98	C₆H₅CO (3a)	4f	69	79∶21	97
7	4-O₂NC₆H₄ (2g)	98	C₆H₅CO (3a)	4g	70	80∶20	98
8	4-CF₃C₆H₄ (2h)	98	C₆H₅CO (3a)	4h	80	78∶22	97
9	4-CH₃C₆H₄ (2i)	97	C₆H₅CO (3a)	4i	70	95∶5	97
10^f	4-CH₃OC₆H₄ (2j)	—	C₆H₅CO (3a)	4j	72	87∶13	—
11^f	2-Pyridyl (2k)	—	C₆H₅CO (3a)	4k	38	>20∶1	—
12	C₆H₅ (2a)	98	4-CH₃OC₆H₄CO (3b)	4l	71	91∶9	97
13	C₆H₅ (2a)	98	4-F₃CC₆H₄CO (3c)	4m	80	94∶6	98
14	C₆H₅ (2a)	98	C₆H₅ (3d)	4n	45	83∶17	97

Entry	R¹	ee^b/%	R² (3)	Main product	Total yield^c/%	4∶5^d	ee^e/%
1	C₆H₅ (2a)	98	C₆H₅CO (3a)	4a	86	92∶8	97
2	2-ClC₆H₄ (2b)	97	C₆H₅CO (3a)	4b	65	82∶18	93
3	3-ClC₆H₄ (2c)	95	C₆H₅CO (3a)	4c	90	80∶20	93
4	4-ClC₆H₄ (2d)	99	C₆H₅CO (3a)	4d	94	87∶13	93
5	4-BrC₆H₄ (2e)	96	C₆H₅CO (3a)	4e	94	91∶9	95
6	4-NCC₆H₄ (2f)	98	C₆H₅CO (3a)	4f	69	79∶21	97
7	4-O₂NC₆H₄ (2g)	98	C₆H₅CO (3a)	4g	70	80∶20	98
8	4-CF₃C₆H₄ (2h)	98	C₆H₅CO (3a)	4h	80	78∶22	97
9	4-CH₃C₆H₄ (2i)	97	C₆H₅CO (3a)	4i	70	95∶5	97
10^f	4-CH₃OC₆H₄ (2j)	—	C₆H₅CO (3a)	4j	72	87∶13	—
11^f	2-Pyridyl (2k)	—	C₆H₅CO (3a)	4k	38	>20∶1	—
12	C₆H₅ (2a)	98	4-CH₃OC₆H₄CO (3b)	4l	71	91∶9	97
13	C₆H₅ (2a)	98	4-F₃CC₆H₄CO (3c)	4m	80	94∶6	98
14	C₆H₅ (2a)	98	C₆H₅ (3d)	4n	45	83∶17	97

卤盐催化的α,β-环氧羧酸酯与异氰酸酯[3＋2]环加成反应研究