Control of Properties of Cage-Shaped Metal Complexes

笼状金属配合物性能的控制

• 批准号: 21350074
• 负责人: YASUDA Makoto
• 金额: $ 12.48万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2009
• 资助国家: 日本
• 起止时间: 2009 至 2011
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-21350074/
• 关键词: 立体規制; ルイス酸; ホウ素; ケイ素; 触媒; 選択的反応; ガリウム; 錯体; ホウ酸

New type of cage-shaped metal complexes were prepared and applied to Lewis acid chemistry. Our original type of the complex has B(C6H4) 3CH. We modified it to silicon-including type. The complexes with various substituents(electron-withdrawing or donating groups) has been also synthesized. A careful investigation of ligand-dissociation rate on the complexes clarified the tuning factor that is classified into steric and electronic factors. DFT calculation revealed the LUMO energies that contribute to Lewis acid-catalyzed reactions. In fact, some organic transformations using the complexes as a Lewis acid have been employed.

制备了新型笼状金属配合物并将其应用于路易斯酸化学。我们最初的配合物类型是 B(C6H4) 3CH。我们将其修改为含硅类型。还合成了具有各种取代基（吸电子基团或供电子基团）的配合物。对配合物的配体解离速率的仔细研究阐明了分为空间因素和电子因素的调节因素。 DFT 计算揭示了路易斯酸催化反应的 LUMO 能量。事实上，已经采用了一些使用配合物作为路易斯酸的有机转化。

项目成果

Indium Tribromide Catalyzed Cross-Claisen Condensation between Carboxylic Acids and Ketene Silyl Acetals Using Alkoxyhydrosilanes

使用烷氧基氢硅烷，三溴化铟催化羧酸与烯酮甲硅烷基缩醛之间的交叉克莱森缩合

• DOI: 10.1002/anie.201104140
• 发表时间: 2011
• 作者: 西木能弘

Regio- and Stereoselective Generation of Alkenylindium Compounds from Indium Tribromide, Alkynes, and Ketene Silyl Acetals

从三溴化铟、炔烃和烯酮甲硅烷基缩醛区域选择性和立体选择性生成烯基铟化合物

• 发表时间: 2009
• 作者: 西本能弘

Characterization of the Nucleophilic Allylindium Species Generated from Allyl Bromide and Indium(0) in Aqueous Media

水介质中烯丙基溴和铟 (0) 生成的亲核烯丙基物种的表征

• DOI: 10.1002/ejoc.201000956
• 发表时间: 2010-10-01
• 期刊: European Journal of Organic Chemistry
• 影响因子: 2.8
• 作者: M. Yasuda;Masa;Y. Nagaoka;A. Baba
• 通讯作者: A. Baba

Cyclopropylmethylation of Benzylic and Allylic Chlorides with Cyclopropylmethylstannane Catalyzed by Gallium or Indium Halide

镓或卤化铟催化环丙基甲基锡烷对苄基和烯丙基氯进行环丙基甲基化

• 发表时间: 2010
• 作者: 清川謙介

Alkylindium Species for Coupling Reaction with Organic Halides in a Radical Manner

用于与有机卤化物进行自由基偶联反应的烷基铟物种

• 发表时间: 2011
• 作者: 安田誠;馬場章夫
• 通讯作者: 馬場章夫