Copper-catalyzed Intramolecular Aminoperfluoroalkylation Reaction of O-Homoallyl Benzimidates

doi:10.6023/A19060220

Acta Chimica Sinica ›› 2019, Vol. 77 ›› Issue (9): 884-888.DOI: 10.6023/A19060220 Previous Articles Next Articles

Special Issue: 有机自由基化学；纪念南开大学化学学科创建100周年

Communication

铜催化苯甲酰亚胺高烯丙酯的分子内胺化全氟烷基化反应

张衡, 牟学清, 陈弓^*(), 何刚^*()

南开大学化学学院元素有机化学国家重点实验室天津 300071

投稿日期:2019-06-18 发布日期:2019-08-13
通讯作者: 陈弓,何刚 E-mail:gongchen@nankai.edu.cn;hegang@nankai.edu.cn
基金资助:
项目受国家自然科学基金(Nos.21672105);项目受国家自然科学基金(21702109);项目受国家自然科学基金(21890722);天津市自然科学基金(Nos.17JCYBJC19700);天津市自然科学基金(18JCZDJC32800);南开大学中央高校基本科研业务费专项资金资助(No.63161122)

Copper-catalyzed Intramolecular Aminoperfluoroalkylation Reaction of O-Homoallyl Benzimidates

Zhang, Heng, Mou, Xueqing, Chen, Gong^*(), He, Gang^*()

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071

Received:2019-06-18 Published:2019-08-13
Contact: Chen, Gong,He, Gang E-mail:gongchen@nankai.edu.cn;hegang@nankai.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China(Nos.21672105);Project supported by the National Natural Science Foundation of China(21702109);Project supported by the National Natural Science Foundation of China(21890722);Natural Science Foundation of Tianjin(Nos.17JCYBJC19700);Natural Science Foundation of Tianjin(18JCZDJC32800);the Fundamental Research Funds for the Central Universities (Nankai University)(No.63161122)

1. Copper-catalyzed Intramolecular Aminoperfluoroalkylation Reaction of O-Homoallyl Benzimidates.PDF(10912KB)

Abstract

Azaheterocycles have been broadly applied in the development of therapeutic agents, agrochemicals and functional material molecules. Azaheterocycles equipped with perfluoroalkyl group usually manifest superior physical and biological properties than their parent molecules, such as showing improved metabolic stability and high lipophilicity. The synthesis of perfluoroalkyl modified azaheterocycles has attracted considerable research interest in recent years. The strategy of intramolecular aminoperfluoroalkylation of alkenes, which functionalize C=C bond with an external perfluoroalkyl group and an internal amine nucleophile in one pot, provides a streamlined synthesis of perfluoroalkyl substituted azaheterocycles. This strategy has been applied by Liu, Sodeoka and other research groups in the synthesis of perfluoroalkyl substituted aziridines, pyrrolidines, lactams and pyrazolines featuring the use of pendent amine, amide, hydrazone or urea group as internal amine source. We have previously developed a copper(I)-catalyzed intramolecular aminotrifluoromethylation reaction of O-homoallyl benzimidates with Togni reagent I for the synthesis of trifluoromethyl containing chiral 1,3-oxazines using a chiral BOX ligand. However, this method is limited to aminotrifluoromethylation reaction as other perfluoroalkyl substituted hypervalent iodine reagents are not easily accessible. Herein, we report our recent research results on the synthesis of perfluoroalkyl substituted 1,3-oxazines using commercial available perfluoroalkyl iodides as perfluoroalkyl source. This intramolecular aminoperfluoroalkylation reaction proceeds selectively in the presence of Cu(OAc)₂ catalyst, 1,10-phenanthroline ligand and AgOAc additive. A broad range of O-homoallyl benzimidates and perfluoroalkyl iodides are compatible with the reaction conditions, affording perfluoroalkyl substituted 1,3-oxazines in moderate to good yields. The 1,3-oxazine product can be prepared in gram scale and readily hydrolyzed under mild conditions to give perfluoroalkyl substituted 1,3-amino alcohols. Preliminary mechanism studies revealed that this intramolecular aminoperfluoroalkylation reaction initiated with the addition of a perfluoroalkyl radical to the terminal alkene, and the subsequent functionalization with the benzimidate motif via intramolecular substitution generated 1,3-oxazine products.

Key words: O-homoallyl benzimidates, aminoperfluoroalkylation, perfluoroalkyl iodides, 1,3-oxazines, copper catalysis

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Zhang, Heng, Mou, Xueqing, Chen, Gong, He, Gang. Copper-catalyzed Intramolecular Aminoperfluoroalkylation Reaction of O-Homoallyl Benzimidates[J]. Acta Chimica Sinica, 2019, 77(9): 884-888.

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铜催化苯甲酰亚胺高烯丙酯的分子内胺化全氟烷基化反应

Copper-catalyzed Intramolecular Aminoperfluoroalkylation Reaction of O-Homoallyl Benzimidates

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Entry	Catalyst	Additive	Solvent	Yield^a/% of 2
1^b	Cu(CH₃CN)₄PF₆	BOX ligand	DCE	NR
2	Cu(CH₃CN)₄PF₆	AgOAc	DCE	44
3	CuCl	AgOAc	DCE	54
4	CuBr	AgOAc	DCE	62
5	CuI	AgOAc	DCE	60
6	Cu(acac)₂	AgOAc	DCE	54
7	Cu(OTf)₂	AgOAc	DCE	45
8	Cu(OAc)₂	AgOAc	DCE	72 (64)^c
9	Cu(OAc)₂	AgOTFA	DCE	19
10	Cu(OAc)₂	AgOTf	DCE	47
11	Cu(OAc)₂	Ag₂CO₃	DCE	53
12	Cu(OAc)₂	Cs₂CO₃	DCE	20
13	Cu(OAc)₂	AgOAc	CH₃CN	67
14	Cu(OAc)₂	AgOAc	THF	52
15	Cu(OAc)₂	AgOAc	EtOAc	63
16	Cu(OAc)₂	—	DCE	NR
17		AgOAc	DCE	<5
18^d	Cu(OAc)₂	AgOAc	DCE	<5
19^e	Cu(OAc)₂	AgOAc	DCE	53

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