Design of metal-catalyzed synthetic reactions based on theoretical calculations

基于理论计算的金属催化合成反应设计

• 批准号: 17550103
• 负责人: YAMABE Shinichi
• 金额: $ 2.3万
• 依托单位: Nara University of Education
• 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-17550103/
• 关键词: Organic chemistry; Reaction mechanism; Computational chemistry; Friedel-Crafts Reaction; Density functional theory; Disilene; Hydrogen bond; 水素1,5-シフト; Beckmann転位; ベンジル-ベンジル酸転位; 芳香族求電子置換反応; エナンチオ選択的付加

1) The Friedel-Crafts reaction is a representative electrophilic aromatic substitution reaction, catalyzed by Lewis acids. The precise reaction mechanism has not been elucidated yet. Understanding of catalytic ability of the bridged form of a typical Lewis acid Al_2Cl_6, the driving force for proton elimination of Wheland intermediate, and rate-determining step is required. B3LYP density functional theory calculations with 6-31G^* basis set of Friedel-Crafts aclylation reaction of benzene with acetyl chloride catalyzed by aluminum chloride were carried out. At first, carbonyl oxygen coordinates to Al and the resulting complex isomerizes to acylium ion intermediate (π-complex). After the electrophilic addition, Wheland intermediate (σ-complex) forms. Thus, the elementary process was elucidated. The study on Friedel-Crafts alkylation is currently under investigation.2) Density functional and ONIOM calculations of alcohol and phenol additions to two (tetramethyl and tetramesityl) dislenes were carried out. The dimer of MeOH adds to Me_2Si = SiMe_2 more readily than the monomer. The trimer gives not the adduct but a zwitter-ionic intermediate. In the (CF_3OH)_2 addition to Me_2Si = SiMe_2, the H......Si bond formation is more advanced than the O....Si bond formation at the transition state (TS). Additions of seven phenol derivatives to Me_2Si = SiMe_2 were examined, and the dimer reactions were found to be better than the monomer reaction regardless of the substituents on benzene rings. (MeOH)_2 reacts also with Mes_2Si = SiMes_2 favorably, and an isomer of the reactant like complex (precursor) may afford an adduct of the different stereochemistry via internal rotations. Generally, the dimer of the alcohol or phenol is the reactant toward the disilenes. Exceptionally, a monomer of p-(dimethylamino)phenol reacts with Mes_2Si = SiMes_2 owing to the steric congestion by four mesityl groups.

1）弗里德尔（Friedel-Crafts）复制反应。氯化铝含量。当前正在研究中。2）密度的功能和两个IED的酒精添加到MEOH的二聚体中。在ME_2SI = SIME_2中添加了七个苯酚衍生物，发现二聚体反应比苯二元组上的单体后期更好四个Mesityl群体朝向空间充血。

项目成果

Surface structures, photovoltages, and stability of n-Si(111) electrodes surface modified with metal nanodots and various organic groups.

• DOI: 10.1021/la050423k
• 发表时间: 2005-09
• 期刊: Langmuir : the ACS journal of surfaces and colloids
• 作者: Susumu Takabayashi;M. Ohashi;K. Mashima;Yang Liu;S. Yamazaki;Y. Nakato

Catalytic enantioselective Friedel-Crafts/Michael addition reactions of indoles to ethenetricarboxylates.

• DOI: 10.1021/jo052041p
• 发表时间: 2006-01
• 期刊: The Journal of organic chemistry
• 作者: S. Yamazaki;Y. Iwata

Novel Lactonization of Ethenetricarboxylate Derivatives : Intermolecular Trapping of Alkenes.

乙烯三羧酸酯衍生物的新型内酯化：烯烃的分子间捕获。

• 发表时间: 2005
• 期刊: Org. Lett. 7
• 作者: Yamazaki;S.
• 通讯作者: S.

A Lewis-acid catalyzed synthesis of substituted oxindole derivatives.

路易斯酸催化合成取代的羟吲哚衍生物。

• 发表时间: 2006
• 期刊: Heterocycles 67
• 作者: Yamazaki;S.
• 通讯作者: S.

Is the Beckmann rearrangement a concerted or stepwise reaction? A computational study.

• DOI: 10.1021/jo0508346
• 发表时间: 2005-11
• 期刊: The Journal of organic chemistry
• 作者: S. Yamabe;N. Tsuchida;S. Yamazaki