烯酸在碘化铵催化作用下的卤代内酯化反应

doi:10.7503/cjcu20130535

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (2): 286.doi: 10.7503/cjcu20130535

烯酸在碘化铵催化作用下的卤代内酯化反应

朱敏(), 金建昌, 张慧

浙江树人大学生物与环境工程学院, 杭州 310015

收稿日期:2013-06-05 出版日期:2014-02-10 发布日期:2013-07-29
作者简介:联系人简介: 朱敏, 女, 教授, 主要从事有机化学研究. E-mail:hzzm60@163.com
基金资助:
国家自然科学基金(批准号: 21072176)资助

Halolactonization of Alkenoic Acid Catalyzed by Ammonium Iodide^†

ZHU Min^*(), JIN Jianchang, ZHANG Hui

College of Biological and Environmental Sciences, Zhejiang Shuren University, Hangzhou 310015, China

Received:2013-06-05 Online:2014-02-10 Published:2013-07-29
Contact: ZHU Min E-mail:hzzm60@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.21072176)

摘要/Abstract

摘要：

研究了不饱和烯酸在碘化铵催化作用下的溴代和氯代内酯化反应. 通过该反应, 4-戊烯酸等不饱和烯酸在催化剂碘化铵和氧化剂间氯过氧苯甲酸作用下很容易与溴化锂和氯化锂反应, 常温下短时间内即可得到良好产率的溴/氯甲基γ-丁内酯化合物, 从而建立了一个简单快速合成溴/氯甲基γ-丁内酯的新方法. 考察了反应条件对反应的影响, 提出了该反应是经过有机高价碘中间体而进行的反应机理.

关键词: 催化内酯化反应, 有机高价碘中间体, 碘化铵, 4-戊烯酸

Abstract:

A novel halolactonization of pentenoic acids was developed, which was catalyzed by hypervalent iodine species generated in situ from ammonium iodide. In this protocol, 4-pentenoic acids reacted easily with lithium bromide or lithium chloride under catalyst ammonium iodide in combination with m-chloroperbenzoic acid(mCPBA) as the terminal oxidant in CH₃CN at room temperature, which provided five-membered halolactones in moderate to good yields. A new plausible reaction pathway for the reaction was hypothesized. Thus, NH₄I was first oxidized to I₂ and HOI with mCPBA, both of them reacted with alkenoic acid to form the iodolactone, which then was transformed into the hypervalent iodine intermediate in situ by the continuing oxidation, and finally the halolactone was provided when lithium bromide or lithium chloride was acted as nucleophile in the following intermolecular nucleophilic substitution. This method has some advantages such as mild reaction conditions, simple procedure and good yields. Furthermore, the scope of hypervalent iodine reagents in organic synthesis could be extended.

Key words: Catalytic halolactonization, Hypervalent iodine intermediate, Ammonium iodide, 4-Pentenoic acid

中图分类号:

O621.3

TrendMD:

朱敏, 金建昌, 张慧. 烯酸在碘化铵催化作用下的卤代内酯化反应. 高等学校化学学报, 2014, 35(2): 286.

ZHU Min, JIN Jianchang, ZHANG Hui. Halolactonization of Alkenoic Acid Catalyzed by Ammonium Iodide^†. Chem. J. Chinese Universities, 2014, 35(2): 286.

图/表 5

参考文献 41

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Entry	n(LiBr)/mmol	n(NH₄I)/mmol	n(mCPBA)/mmol	Solvent	Time/h	Yield^b(%)
1	1.5	0.1	2.0	CH₂Cl₂	10	45
2	1.5	0.1	2.0	CH₃OH	10	23
3	1.5	0.1	2.0	THF	10	52
4	1.5	0.1	2.0	CF₃CH₂OH	10	67
5	1.5	0.1	2.0	CH₃CN	10	71
6	2.0	0.1	2.0	CH₃CN	10	78
7	3.0	0.1	2.0	CH₃CN	10	79
8	5.0	0.1	2.0	CH₃CN	10	80
9	KBr(2.0)	0.1	2.0	CH₃CN	10	65
10	NaBr(2.0)	0.1	2.0	CH₃CN	10	48
11	NH₄Br(2.0)	0.1	2.0	CH₃CN	10	52
12	2.0	0.2	2.0	CH₃CN	10	77
13	2.0	0.3	2.0	CH₃CN	10	79
14	2.0	0.05	2.0	CH₃CN	10	65
15	2.0	0	2.0	CH₃CN	10	0
16	2.0	KI(0.1)	2.0	CH₃CN	10	51
17	2.0	NaI(0.1)	2.0	CH₃CN	10	63
18	2.0	I₂(0.1)	2.0	CH₃CN	10	66
19	2.0	0.1	NaBO₃(2.0)	CH₃CN	10	5
20	2.0	0.1	Na₂S₂O₈(2.0)	CH₃CN	10	7
21	2.0	0.1	Oxone(2.0)	CH₃CN	10	55
22	2.0	0.1	2.5	CH₃CN	10	84
23	2.0	0.1	3.0	CH₃CN	10	82
24	2.0	0.1	1.5	CH₃CN	10	66
25	2.0	0.1	2.5	CH₃CN	16	85
26	2.0	0.1	2.5	CH₃CN	8	84
27	2.0	0.1	2.5	CH₃CN	6	84
28	2.0	0.1	2.5	CH₃CN	3	68

Entry	n(LiBr)/mmol	n(NH₄I)/mmol	n(mCPBA)/mmol	Solvent	Time/h	Yield^b(%)
1	1.5	0.1	2.0	CH₂Cl₂	10	45
2	1.5	0.1	2.0	CH₃OH	10	23
3	1.5	0.1	2.0	THF	10	52
4	1.5	0.1	2.0	CF₃CH₂OH	10	67
5	1.5	0.1	2.0	CH₃CN	10	71
6	2.0	0.1	2.0	CH₃CN	10	78
7	3.0	0.1	2.0	CH₃CN	10	79
8	5.0	0.1	2.0	CH₃CN	10	80
9	KBr(2.0)	0.1	2.0	CH₃CN	10	65
10	NaBr(2.0)	0.1	2.0	CH₃CN	10	48
11	NH₄Br(2.0)	0.1	2.0	CH₃CN	10	52
12	2.0	0.2	2.0	CH₃CN	10	77
13	2.0	0.3	2.0	CH₃CN	10	79
14	2.0	0.05	2.0	CH₃CN	10	65
15	2.0	0	2.0	CH₃CN	10	0
16	2.0	KI(0.1)	2.0	CH₃CN	10	51
17	2.0	NaI(0.1)	2.0	CH₃CN	10	63
18	2.0	I₂(0.1)	2.0	CH₃CN	10	66
19	2.0	0.1	NaBO₃(2.0)	CH₃CN	10	5
20	2.0	0.1	Na₂S₂O₈(2.0)	CH₃CN	10	7
21	2.0	0.1	Oxone(2.0)	CH₃CN	10	55
22	2.0	0.1	2.5	CH₃CN	10	84
23	2.0	0.1	3.0	CH₃CN	10	82
24	2.0	0.1	1.5	CH₃CN	10	66
25	2.0	0.1	2.5	CH₃CN	16	85
26	2.0	0.1	2.5	CH₃CN	8	84
27	2.0	0.1	2.5	CH₃CN	6	84
28	2.0	0.1	2.5	CH₃CN	3	68

烯酸在碘化铵催化作用下的卤代内酯化反应

Halolactonization of Alkenoic Acid Catalyzed by Ammonium Iodide^†

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烯酸在碘化铵催化作用下的卤代内酯化反应

Halolactonization of Alkenoic Acid Catalyzed by Ammonium Iodide†

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Halolactonization of Alkenoic Acid Catalyzed by Ammonium Iodide^†