Sterically and Electronically Designed Metal Species for Reactions

用于反应的空间和电子设计金属物质

• 批准号: 17550102
• 负责人: YASUDA Makoto
• 金额: $ 2.24万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17550102/
• 关键词: Lewis acid; Indium; Boron; Silicon; Cage-Shape; Steric Effect; Selectivity; Catalyst

A structurally strained borate was generated in the reaction of tris(2-hydoxyphenyl)methane with borane. The formed boron species has a cage-shape and a pyramidal structure around the boron metal. The cage-shape and structural strain enhance the Lewis acidity and catalytic turn-overs. The cage-shaped borate catalyzed the allylation of benzaldehyde with allyltributyltin, while phenyl borate B(OPh)_3,which has a planar structure, did not show catalytic acitivity. Its pyridine complex was analyzed by NMR which shows strong interaction of the borate with pyridine and a tetrahedral structure around the metal. The pyridine complex in solid state was characterized by X-ray crystallography. Boron has a tetrahedral coordination sphere with the average of bond angles (O-B-O,114.2(9)° and N-B-O,104.1(9)°). The structure without pyridine shows C_3 symmetry. The aromatic rings deviate from a perpendicular plane to that of three oxygens (ca.19.2°) and thus, the pyridine-complex has chiality that is caused by the cage-shape.The combined Lewis acid system using indium and silicon showed very high activity of some reactions. An NMR study clearly showed the interaction of the indium with silicon mediated by Cl as a bridged atom. The high Lewis acidity showed up on the silicon center in situ. The high oxophilicity accelerated the direct subsitution of alcohols in a catalytic manner. The catalyst system accomplished the catalytic substitution of alcohols in a halogen-free solvent. The system is considered to be an ideal and practical process for industrial chemisty.

结构紧张的硼酸盐是用硼烷生成的Tris（2-羟基苯基）甲烷。用烯丙基丁基催化苯甲醛的蛋白质，而苯基硼酸盐B_3 CH具有平面结构，并未显示出催化性的阳性固态中的吡啶型复合物的表征是X射线的，具有键角的平均值（O-B-O，114.2（9）°和N-B-O，104.1（9）°）。从垂直的平面三个氧气），因此，吡啶 - 复合物具有由笼子形状引起的，使用粘合剂和硅的组合液体显示出硅质的含量高的酸度在原位硅中出现。

项目成果

Indium-silicon combined lewis acid catalyst for direct allylation of alcohols with allyltrimethylsilane in non-halogenated solvent

• DOI: 10.1055/s-2005-869878
• 发表时间: 2005-07-07
• 期刊: SYNLETT
• 影响因子: 2
• 作者: Saito, T;Yasuda, M;Baba, A
• 通讯作者: Baba, A

Michael Addition of Ketone Enolates to Reductive Cross-Aldol Reaction Using Bromoaldehyde and an Aldehyde Mediated by Germanium(II) : One-Pot, Large-Scale Protocol

使用溴醛和锗 (II) 介导的醛进行酮烯醇化还原交叉羟醛反应的迈克尔加成：一锅法大规模方案

• 发表时间: 2005
• 期刊: Org.Lett. 7
• 作者: Makoto Yasuda;Shin-ya Tanaka;Akio Baba
• 通讯作者: Akio Baba

Practical and Simple Synthesis of Substituted Quinolines by an HC1-DMSO System on a Large Scale : Remarkable Effect of the Chloride Ion

HC1-DMSO 系统大规模实用、简单合成取代喹啉：氯离子的显着效果

• 发表时间: 2006
• 期刊: J.Org.Chem. 71
• 作者: Shin-ya Tanaka;Makoto Yasuda;Akio Baba
• 通讯作者: Akio Baba

Practical and Simple Synthesis of Substituted Quinolines by an HCI-DMSO System on a Large Scale : Remarkable Effect of the Chloride Ion

HCI-DMSO 系统大规模实用、简单合成取代喹啉：氯离子的显着效果

• 发表时间: 2006
• 期刊: J.Org.Chem. 71,2
• 作者: Yamazaki;S.Ohmitsu;K.Ohi;K.Otsubo;T.Moriyama;K.;田中 真哉
• 通讯作者: 田中 真哉

In- or In(I)-employed tailoring of the stereogenic centers in the Reformatsky-type reactions of simple ketones, α-alkoxy ketones, and β-keto esters

• DOI: 10.1021/jo051659w
• 发表时间: 2005-12-09
• 期刊: JOURNAL OF ORGANIC CHEMISTRY
• 影响因子: 3.6
• 作者: Babu, SA;Yasuda, M;Baba, A
• 通讯作者: Baba, A