Copper-Catalyzed Cyclization of Oxime Acetates with 2-Benzylidenemalononitriles for Synthesis of 2?Aminonicotinonitriles

doi:10.6023/A14040263

Acta Chimica Sinica ›› 2014, Vol. 72 ›› Issue (8): 914-919.DOI: 10.6023/A14040263 Previous Articles Next Articles

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铜(I)催化条件下酮肟衍生物与苄烯丙二腈的环化反应构建2-氨基吡啶

蔡忠建, 陆新谋, 汪顺义, 纪顺俊

苏州大学材料与化学化工学部苏州 215123

投稿日期:2014-04-09 发布日期:2014-06-05
通讯作者: 汪顺义, 纪顺俊 E-mail:shunyi@suda.edu.cn;shunjun@suda.edu.cn
基金资助:
项目受国家自然科学基金（No. 21172162）、国家青年自然科学基金（No. 21202111）及江苏省青年自然科学基金（No. BK2012174）资助

Copper-Catalyzed Cyclization of Oxime Acetates with 2-Benzylidenemalononitriles for Synthesis of 2?Aminonicotinonitriles

Cai Zhongjian, Lu Xinmou, Wang Shunyi, Ji Shunjun

Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and MaterialsScience, Soochow University, Suzhou 215123

Received:2014-04-09 Published:2014-06-05
Supported by:
Project supported by Natural Science Foundation of China (No. 21172162), Young National Natural Science Foundation of China (No. 21202111) and Young Natural Science Foundation of Jiangsu Province (No. BK2012174).

1. Copper-Catalyzed Cyclization of Oxime Acetates with 2-Benzylidenemalononitriles for Synthesis of 2?Aminonicotinonitriles.PDF(4442KB)

Abstract

The 2-aminopyridine is the core structure of many potential drug candidates for the treatment of a variety of disorders. It is widely used as building block for the synthesis of series nitrogen-containing heterocycles. However, the traditional synthesis of 2-aminopyridines relies on amination of 2-unsubstituted pyridines with sodium amide which is limited to low yield and narrow scope for the using of strongly basic conditions. Oximes and their derivatives are a class of powerful building blocks in organic synthesis. Recently, a series of reports are focus on copper-catalyzed cyclization of oxime esters, and various methods are developed for the construction of five- or six-membered heterocycles. Based on our sustained efforts to copper-catalyzed cyclization for access to heterocyles, we herein report a novel process of copper-catalyzed cyclization of oxime esters with 2-benzylidenemalononitrile for the construction of 2-aminopyridines. Various 2-aminopyridines were obtained in middle to good yields under the optimized reaction conditions. In this case, the N—O bond cleavage would occur for oxime esters reduced by copper(I) catalyst, followed by the formation of nucleophilic copper(II) enamide which serve as a precursor in heterocycle synthesis. A representative procedure for the copper-catalyzed construction of 2-aminopyridines by cyclization of oxime esters with 2-benzylidenemalononitrile is as following: The substrate acetophenone O-acetyl oxime (1a, 0.5 mmol, 0.0885 g), 2-benzylidenemalononitrile (2a, 0.5 mmol, 0.0770 g), CuCl (0.1 mmol, 0.0989 g, 20 mol%), and NaHSO₃ (1.0 mmol, 0.1041 g) were added to a 10 mL Schlenk tube, followed by addition of DMF (dried by calcium hydride and freshly distilled, 3 mL). The mixture was stirred at 60 ℃ as monitored by TLC. The solution was then quenched by H₂O and extracted with EtOAc (20 mL×3), the combined organic layers were dried over Na₂SO₄, filtered, and evaporated under vaccum. The residue was purified by column chromatography on silica gel (eluent: light petroleum ether:ethyl acetate, V:V=5:1) to afford the desired product 4,6-diphenylpyridin-2-amine 3a.

Key words: copper, oxime esters, 2-benzylidenemalononitrile, cyclization, 2-aminopyridine

Cite this article

Cai Zhongjian, Lu Xinmou, Wang Shunyi, Ji Shunjun. Copper-Catalyzed Cyclization of Oxime Acetates with 2-Benzylidenemalononitriles for Synthesis of 2?Aminonicotinonitriles[J]. Acta Chimica Sinica, 2014, 72(8): 914-919.

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铜(I)催化条件下酮肟衍生物与苄烯丙二腈的环化反应构建2-氨基吡啶

Copper-Catalyzed Cyclization of Oxime Acetates with 2-Benzylidenemalononitriles for Synthesis of 2?Aminonicotinonitriles

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