Development of new, simple and general synthetic methods of useful heterocyclic compounds

开发有用杂环化合物的新的、简单的和通用的合成方法

• 批准号: 15550092
• 负责人: KOBAYASHI Kazuhiro
• 金额: $ 2.05万
• 依托单位: Tottori University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550092/
• 关键词: quinoline; isocyanide; styrene; indole; quinone; enolate; iodocyclization; thiophene; ベンズアゼチン; チエノベンゾフランキノン; キノロン; ナフトチオフェンキノン; インドロキノリン; ベンゾジオキシノン; 光反応; ピラン; フロオキセピン; イソインドリン; マグネシウムアミド; イソキノリン; ニトリル; ベンジルアニオン; 有機リチウム; リチウムアミド

First, two new and efficient methods for the preparation of quinoline derivatives were developed. The first method is based on reactions of 2-isocyanostyrene derivatives with electrophiles, such as aldehydes, ketones, and aldehydes, in the presence of a Lewis acid. The second method is based on reactions of 2-isocyano-β-methoxystyrene derivatives with organolithiums and lithium dialkylamides. As an application of the former method, 11H-indolo[3,2-c]quinolines carrying a functional group at the 6-position were prepared by electorophile-mediated cyclization of 2-(2-isocyanophenyl)-1-methyl-1H-indole. As an application of the latter method, isoquinoline derivatives were prepared by reactions of 2-cyano-β-methoxystyrene derivatives with organolithiums and lithium dialkylamides.Next, new syntheses of heterocycke-fused quinines, such as 1H,5H-pyrano[3,4-f]indole-4,9-dione,12-hydroxy-12H-thioxanthene-6,11-dione,thieno[2,3-f]benzofuran-4,8-dione,thieno[3,2-g]benzofuran-4,5-dione, and naphtho[1,2-b]thiophene-4,5-dione derivatives, were accomplishedFurthermore, utilizing reactions of various enolates with lactones and nitriles, 3,6,7,8-tetrahydro[3,2-c]oxepin-4(2H)-one, (3-iminoisoindolin-1-ylidene)carboxylic ester, and 3-(1-aminoalkyl)quinolin-2(1H)-one derivatives were prepared.Lastly, benzazetine and 4H-1,3-benzodioxin-2-one derivatives were prepared by iodocyclization of appropriately o-substituted styrene derivatives.

首先，开发了两种新的高效制备喹啉类化合物的方法。第一种方法是基于2-异氰基苯乙烯衍生物在Lewis酸存在下与亲电性物质，如醛、酮和醛的反应。第二种方法是基于2-异氰基-β-甲氧基苯乙烯衍生物与有机硫和二烷基胺锂的反应。作为前者的应用，通过亲电催化环化2-(2-异氰苯基)-1-甲基-1H-吲哚，合成了6-位带有官能团的11H-吲哚并[3，2-c]喹啉类化合物。作为后一种方法的应用，通过2-氰基-β-甲氧基苯乙烯衍生物与有机锂和二烷胺的反应合成了异喹啉衍生物。其次，利用不同烯醇类化合物与内酮和腈的反应，合成了新的杂环稠合奎宁，如Thieno[2，3-f]苯并呋喃-4，8-二酮、Thieno[3，2-g]苯并呋喃-4，5-二酮和萘并[1，2-b]噻吩二酮衍生物合成了7，8-四氢[3，2-c]奥西平-4(2H)-酮、(3-亚氨基异吲哚-1-亚甲基)羧酸酯和3-(1-氨基烷基)喹啉-2(1H)-酮衍生物。

项目成果

小林和裕: "New synthesis of isoquinoline derivatives by reactions of 2-(2-methoxy-ethenyl)benzonitriles with organolithiums and lithium dialkylamides"Chemistry Letters. 33・3. 236-267 (2004)

Kazuhiro Kobayashi：“通过 2-(2-甲氧基-乙烯基)苯甲腈与有机锂和二烷基酰胺锂反应的异喹啉衍生物的新合成”，化学快报 33・3 (2004)。

New Synthesis of Isoquinoline Derivatives by Reactions of 2-(2-Methoxyethenyl)benzonitriles with Organolithiums and Lithium Dialkylamides

• DOI: 10.1246/cl.2004.236
• 发表时间: 2004-01
• 期刊: Chemistry Letters
• 影响因子: 1.6
• 作者: K. Kobayashi;Taiyo Shiokawa;Osamu Morikawa;H. Konishi

An efficient synthesis of 2,4-disubstituted quinolines by electrophile-mediated cyclization reactions of 2-isocyanostyrene derivatives

• DOI: 10.1246/bcsj.77.553
• 发表时间: 2004-03
• 期刊: Bulletin of the Chemical Society of Japan
• 影响因子: 4
• 作者: K. Kobayashi;Kenichi Takagoshi;S. Kondo;Osamu Morikawa;H. Konishi

A simple Synthesis of 4H-1,3-Benzodioxin-2-one Derivatives by Iodocyclization of t-Butyl o-Vinylphenyl Carbonate Derivatives

叔丁基邻乙烯基苯基碳酸酯衍生物碘环化简单合成4H-1,3-苯并二恶英-2-酮衍生物

• 发表时间: 2006
• 期刊: Bulletin of the Chemical Soiety of Japan 79・3
• 作者: 小林和裕

Reactions of a 5-Hydroxymethyl-1H-indole-4,7-dione with Enamines for the First Construction of 1H,5H-Pyrano[3.4-f]indole-4,9-dione Derivatives

5-羟甲基-1H-吲哚-4,7-二酮与烯胺的反应首次构建1H,5H-吡喃并[3.4-f]吲哚-4,9-二酮衍生物

• 发表时间: 2004
• 期刊: Heterocycles 63・7
• 作者: 小林和裕;Kazuhiro Kobayashi;小林和裕;小林和裕;小林和裕;小林和裕;小林和裕;小林和裕;小林和裕;Kazuhiro Kobayashi;Kazuhiro Kobayashi;Kazuhiro Kobayashi;Kazuhiro Kobayashi;Kazuhiro Kobayashi;Kazuhiro Kobayashi;小林和裕;小林和裕;小林和裕;小林和裕;小林和裕;小林和裕;小林和裕;小林和裕;小林和裕;Kazuhiro Kobayashi;Kazuhiro Kobayashi;Kazuhiro Kobayashi;Kazuhiro Kobayashi;Kazuhiro Kobayashi;Kazuhiro Kobayashi;小林和裕
• 通讯作者: 小林和裕