Transformation of Alcohols ; Development of Substitution of Hydroxyl Groups

醇的转化；

基本信息

批准号：
16350056
负责人：
BABA Akio
金额：
$ 9.98万
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：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-16350056/
关键词：
Lewis acid Indium Silicon Alcohol Substitution NMR Selectivity Catalyst 置換直接変換水酸基塩素化

项目摘要

Alcohols are the most abundant chemicals and should be useful for chemical industry. However, low leaving ability of OH groups retards the development of chemistry based on alcohols. In this research, catalytic subsutition of alcohols was accomplished using indium-silicon combined system. The key species in the catalyst supplies Lewis acid center on silicon in situ. The alkylation reagens have wide application with allylsilane, alkynylsilane, or prennylsilanes. This system showed high chemoselectivity; ester, halo, nitro groups were intert to the reaction system. The used solvent can be hexane that is not halogenated on e although the reported examples by others should use halogenated solvents for catalytic alcohol substitution. This fact strongly contributes to the industrial chemistry based on environmental aspects. The reaction mechanism includes cationic species as a ke y intermediate because tertiary alcohols showed higher reactivity than other alcohols in the reaction system. Therefore, selective alkylation for the compounds bearing primary and tertiary OH groups was well accomplished to give the desired product. This system was also applied to the sugar chemistry. The catalytic substitution of sugar-derivatives by allylsilane in a catalytic manner gave a resource natural product in one-step without any protecting procedures. Even the substrate alcohol has ferrocenic moiety (organometallic part), the reaction proceeded effectively without any effect on the metallo sites. The results described above shows the practical and industrial application for preparation of basic chemicals starting from alcohols. The process will be t he ideal and promising in a future.

醇是最丰富的化学物质，应该对化学工业有用。但是，OH组的较低的离开能力阻碍了基于酒精的化学发展。在这项研究中，使用indium-silicon组合系统完成了醇的催化亚馆。催化剂中的关键物种在原位提供了硅酸中心。烷基化试剂与烯丙基，烷基硅烷或prennylsilanes具有广泛的应用。该系统表现出较高的化学选择性。酯，光环，硝基组与反应系统互动。使用的溶剂可以是己烷，尽管其他人报告的例子应使用卤代溶剂进行催化酒精取代，己烷也未被卤代卤代。这一事实强烈促进了基于环境方面的工业化学。该反应机制包括阳离子物种作为中级中间体，因为高等教育的反应性比反应系统中的其他醇更高。因此，为携带一级和三级OH组的化合物的选择性烷基化非常有成就，可以提供所需的产物。该系统也应用于糖化学。烯丙基硅烷以催化方式催化糖衍生物的催化剂将资源天然产物单步提供，而无需任何保护程序。即使是底物酒精也有铁质合性部分（有机金属部分），反应也有效进行，对金属部位没有任何影响。上面描述的结果表明，从酒精开始制备基本化学物质的实际和工业应用。该过程将是理想的，并有希望的未来。

项目成果

期刊论文数量（57）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Indium-Employed One-Pot Sequential Double Nucleophilic Attack on a Symmetrical DicarboxaldehydeSrinivasarao

使用铟对对称二醛Srinivasarao进行一锅连续双亲核攻击

DOI：
发表时间：
2004
期刊：
Synlett
影响因子：
2
作者：
芝田育也;芝田育也
通讯作者：
芝田育也

Triethylsilane-indium(III) chloride system as a radical reagent

DOI：
10.1021/ol047849v
发表时间：
2004-12-23
期刊：
ORGANIC LETTERS
影响因子：
5.2
作者：
Hayashi, N;Shibata, I;Baba, A
通讯作者：
Baba, A

Direct Chlorination of Alcohols : Synthesis of Ethyl 3-Chloro-3-Phenylpropanoate [Benzenepropanoic acid, b-chloro-, ethylester]

醇的直接氯化：3-氯-3-苯基丙酸乙酯的合成 [苯丙酸，b-氯-乙酯]

DOI：
发表时间：
2006
期刊：
Org. Synth. 83
影响因子：
0
作者：
Ikuya Shibata;Hirofumi Kato;Makoto Yasuda;Akio Baba;Srinivasarao Arulananda Babu;齋藤隆博;加藤洋史;林直樹;Srinivasarao Arulananda Babu;加藤博史;安田誠
通讯作者：
安田誠

In (III)-Mediated Chemoselective Dehydrogenative Interaction of ClMe_2SiH with Carboxylic Acids : Direct Chemo-and Regioselective Friedel-Crafts Acylation of Aromatic Ethers

(III) 介导的 ClMe_2SiH 与羧酸的化学选择性脱氢相互作用：芳香族醚的直接化学和区域选择性傅克酰化