Development and Application of Coupling Reactions via Carbon-Carbon Bond Ceavage

碳-碳键断裂偶联反应的开发与应用

• 批准号: 09440212
• 负责人: TAKAHASHI Tamotsu
• 金额: $ 7.36万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440212/
• 关键词: zirconium; crabon-carbon bond cleavage; zirconacycles; dihalopyridine; quinoline; isoquinoline; zirconacyclopentadienes; ジルコナシクロペンタジュン; ジルコニウム錯体; シルコノセン・エチレン錯体; ジルコナシクロペンテン; 不飽和ケトン; ホモアリルアルコール; 炭素-炭素結合の活性化; 炭素-炭素結合生成反応; 単結晶X線構造解析; 炭素炭素結合切断

When two of unsaturated compounds couple on zirconocene (II), five-membered zirconacycles were formed in high yields. Carbon-carbon bond cleavage of the zirconacycles followed by the second coupling with another unsaturated compounds afforded various types of zirconacycles. In particular, when the direct coupling of two unsaturated compounds is difficult, our method developed is very useful. In this project we developed further useful reactions. Pyridines with two halogens at C2 and C3 carbons reacted with zirconacyclopentadienes in the presence of CuCl, new two carbon-carbon bonds were formed at C2 and C3 carbons. Quinoline derivatives were formed in high yields. When 3,4-dihalopyridines were used, isoquinoline derivatives were obtained in a similar manner. For these reactions, various substituents could be used. Not only monocyclic zirconacyclopentadienes, but also bicyclic zirconacyclopentadienes reacted without any problems.

当两个不饱和化合物夫妇在锆石（II）上（II）时，形成了高产量的五个元素。锆石的碳碳键裂解，然后第二次与另一种不饱和化合物耦合，提供了各种类型的锆囊。特别是，当困难两种不饱和化合物的直接耦合时，我们开发的方法非常有用。在这个项目中，我们开发了进一步的有用反应。在CUCL存在下与锆囊性周期性反应的C2和C3碳中的吡啶，在C2和C3碳中形成了新的两种碳碳键。喹啉衍生物以高产量形成。当使用3,4-二甲吡啶时，以类似方式获得异喹啉衍生物。对于这些反应，可以使用各种取代基。不仅单核酸锆囊性周期性植物，而且双环锆囊卫生​​植物的反应没有任何问题。

项目成果

高橋 保: "Inter or Intramolecular Carbometalation of Non-activated Alkynes by Zirconacyclopentanes in the Presence of Copper Salt"Angew. Chem. Int. Ed. 38. 949-952 (1999)

Tamotsu Takahashi：“铜盐存在下非活化炔烃的分子间或分子内碳金属化”Angew. Ed. 38. 949-952 (1999)

高橋保: "Inter or Intramolecular Carbometalation of Non-activated Alkynes by Zirconacyclopentanes in the Presence of Copper Salt"Augew.Chem. Int.Ed. 38. 949-952 (1999)

Tamotsu Takahashi：“铜盐存在下环戊烷对非活化炔烃的分子间或分子内碳金属化”Augew.Chem. 38. 949-952 (1999)

高橋 保: "A Convenient One-Pot Procedure to Arylcyclobutenes from Arylacetylenes"J. Org. Chem.. 64. 8706-8708 (1999)

Tamotsu Takahashi：“一种从芳基乙炔制备芳基环丁烯的便捷方法”J. Org. 64. 8706-8708 (1999)

TAKAHASHI Tamotsu: "Reaction of Oxazirconacyclopentenes with Propynoates. A New Pathway for the Formation of 2,5-Dihydrofuran Derivatives"Tetrahedron Lett.. 40. 2375-2378 (1999)

高桥保：“氧杂锆环戊烯与丙酸酯的反应。形成 2,5-二氢呋喃衍生物的新途径”Tetrahedron Lett.. 40. 2375-2378 (1999)

高橋 保: "Reaction of Oxazirconacyclopentenes with Propynoates. A New Pathway for the Formation of 2,5-Dihydrofuran Derivatives"Tetrahedron Lett.. 40. 2375-2378 (1999)

Tamotsu Takahashi：“氧杂锆环戊烯与丙酸酯的反应。形成 2,5-二氢呋喃衍生物的新途径”Tetrahedron Lett.. 40. 2375-2378 (1999)