硒介导异腈与邻氨基苯酚环化反应合成2-胺基苯并噁唑

doi:10.6023/cjoc202407001

摘要/Abstract

报道了一种硒粉介导下异腈与邻氨基苯酚进行环化反应合成2-胺基苯并噁唑的方法. 该反应简单地采用硒粉为促进剂, 叔丁醇钠为碱, 在温和条件下实现了多种2-胺基苯并噁唑的绿色、高效构建. 该反应具有操作简便和无金属污染的优点. 该方法还可以实现2-胺基苯并噻唑和2-胺基苯并咪唑的合成.

关键词: 非金属, 硒, 异腈, 邻氨基苯酚, 2-胺基苯并噁唑

Selenium mediated cyclization reaction of isonitriles with o-aminophenols leading to 2-aminobenzoxazoles has been reported. The present method, which simply utilizes element selenium as promoter and ^tBuONa as base, provides a green and efficient approach to synthesize various 2-aminobenzoxazoles under mild conditions. This reaction has the advantages of simple operation and metal-free condition. 2-Aminobenzothiazole and 2-aminobenzimidazole could also be synthesized through this methodology.

Key words: metal-free, selenium, isonitriles, o-aminophenols, 2-aminobenzoxazoles

引用此文

王峥, 兰羽琴, 周芷怡, 谭英姿, 王宗成. 硒介导异腈与邻氨基苯酚环化反应合成2-胺基苯并噁唑[J]. 有机化学, 2025, 45(4): 1379-1385.

Zheng Wang, Yuqin Lan, Zhiyi Zhou, Yingzi Tan, Zongcheng Wang. Selenium Mediated Cyclization Reaction of Isonitriles with o-Aminophenols to Synthesize 2-Aminobenzoxazoles[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1379-1385.

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图/表 7

图1. 具有生物活性的2-胺基苯并噁唑衍生物

Figure 1. Examples of bioactive 2-aminobenzoxazole derivatives

图式1. 邻氨基苯酚与异腈反应合成2-胺基苯并噁唑的方法

Scheme 1. Methods for the synthesis of 2-aminobenzoxazoles from o-aminophenols with isonitriles

Entry	Base (equiv.)	Solvent	T/℃	Yield^b/%
1	K₂CO₃ (1)	DCM	25	23
2	Cs₂CO₃ (1)	DCM	25	5
3	Na₂CO₃ (1)	DCM	25	25
4	K₃PO₄ (1)	DCM	25	26
5	^tBuONa (1)	DCM	25	65
6	DABCO (1)	DCM	25	33
7	Et₃N (1)	DCM	25	26
8	DBU (1)	DCM	25	21
9	^tBuONa (1)	EtOH	25	30
10	^tBuONa (1)	DMF	25	61
11	^tBuONa (1)	1,4-Dioxane	25	20
12	^tBuONa (1)	CH₃CN	25	56
13	^tBuONa (1)	EtOAc	25	0
14	^tBuONa (1)	Toluene	25	0
15	^tBuONa (1)	DMSO	25	76
16	^tBuONa (0.2)	DMSO	25	38
17	—	DMSO	25	trace
18	^tBuONa (1)	DMSO	60	88
19	^tBuONa (1)	DMSO	80	86
20	^tBuONa (1)	DMSO	60	62^c
21	^tBuONa (1)	DMSO	60	21^d
22	^tBuONa (1)	DMSO	60	0^e

表1. 反应条件优化a

Table 1. Optimization of reaction conditions

表2. 合成产物3的底物范围a

Table 2. Substrate scope for the synthesis of product 3

图式2. 克级反应

Scheme 2. Gram-scale synthesis

图式3. 控制实验

Scheme 3. Control experiment

图式4. 可能的反应机理

Scheme 4. Possible reaction mechanism

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