电化学氧化α-酮酸与邻氨基苄胺的脱羧环化反应

doi:10.6023/cjoc202310015

摘要/Abstract

发展了一种无金属、无外加化学氧化剂的条件下, 电化学氧化α-酮酸脱羧与邻氨基苄胺的高效环化反应合成喹唑啉类化合物的方法. 该方法反应条件温和, 底物适用范围广, 以中等到优良的产率得到相应的产物. 同时, 该方法也可以用于苯并噁唑、苯并噻唑和苯并咪唑等杂环的合成.

关键词: 电化学, 氧化脱羧, 环化反应, 喹唑啉

A novel method for synthesizing quinazolines by an electrochemical oxidation decarboxylative cyclization reaction of α-keto acid with o-aminobenzylamine under metal and external chemical oxidants free conditions was developed. This method has mild reaction conditions, and can tolerate a wide range of functional groups, and can provide the corresponding products with moderate to excellent yields. Furthermore, the method can also be used for the synthesis of other heterocycles such as benzoxazole, benzothiazole and benzimidazole.

Key words: electrochemistry, oxidative decarboxylation, cyclization, quinazoline

引用此文

吴际伟, 何俊, 王晶晶, 李丽霞, 徐采玉, 周洁, 李子荣, 许华建. 电化学氧化α-酮酸与邻氨基苄胺的脱羧环化反应[J]. 有机化学, 2024, 44(3): 972-980.

Jiwei Wu, Jun He, Jingjing Wang, Lixia Li, Caiyu Xu, Jie Zhou, Zirong Li, Huajian Xu. Electrochemical Oxidation Decarboxylative Cyclization of α-Keto Acid with o-Aminobenzylamine[J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 972-980.

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图/表 8

图1. 含喹唑啉的药物

Figure 1. Pharmaceuticals containing quinazolines

图式1. 邻氨基苄胺合成喹唑啉的策略

Scheme 1. Diverse synthesis of quinazolines from o-aminobenzylamine

Entry	Variation from the standard conditions	Yield^b/%
1	None	90
2	No electric current	0
3	KI instead of NH₄I	67
4	NH₄Cl instead of NH₄I	84
5	NH₄PF₆ instead of NH₄I	61
6	ⁿBu₄NBF₄ instead of NH₄I	49
7	130 ℃ instead of 120 ℃	90
8	100 ℃ instead of 120 ℃	75
9	80 ℃ instead of 120 ℃	27
10	3 h instead of 4 h	83
11	5 h instead of 4 h	88
12	12 mA instead of 15 mA	80
13	20 mA instead of 15 mA	73
14	CH₃CN instead of DMSO	21
15	THF instead of DMSO	16
16	DMF instead of DMSO	28
17	NMP instead of DMSO	31
18	Platinum plate instead of Graphite rod	66
19	Nickel plate instead of Platinum	74
20	Air instead of N₂	52

表1. 反应条件的优化a

Table 1. Optimization of reaction conditions

表2. 底物的普适性考察a,b

Table 2. Substrate scope of the reaction

图式2. N-取代胺类底物的普适性考察

Scheme 2. N-Substituted amine substrates scope of the reaction

图式3. 合成方法的应用

Scheme 3. Synthetic applications

图式4. 对照实验

Scheme 4. Control experiments

图式5. 可能的反应机理

Scheme 5. Proposed mechanism

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