Development of Oxymethylation Method Utilizing CO of Ambient Pressure

利用常压CO进行羟甲基化方法的开发

基本信息

批准号：
63470081
负责人：
MURAI Shinji
金额：
$ 3.97万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-63470081/
关键词：
Oxymethylation Catalyst Carbon monoxide Transition metal Synthesis CO 炭素骨格変換

项目摘要

Conversion of carbon chain structures and introduction of functional groups are the central aims of organic synthesis. The objective of this project is to develop a new, efficient method of one-carbon chain extension at the desired position of a given organic molecule with concomitant formation of a new functional group on the extended carbon chain. For this purpose, the study of the reaction of organic molecules with a hydrosilane and carbon monoxide with the aid of transition metal catalyst has been undertaken. Emphasis was laid on the study of reaction conditions, since there existed possibility of performing the reaction under very mild conditions such as ambient temperatures and pressures.Among the various catalyst system, complexes containing. cobalt has been found to be the catalyst of choice. Many oxygen and nitrogen containing compounds of various type were subjected to the catalytic reaction system to reveal that a certain kind of reactive oxygen containing compounds was found to react with a hydrosilane and carbon monoxide. Especially, cyclic ethers gave the best results undergoing incorporation of carbon monoxide at ambient temperatures and pressures. The net transformation found was siloxymethylative ring opening, which is a useful but otherwise very difficult synthetic operation. A number of cyclic ethers with a variety of substitution patterns were also subjected to the catalytic system and most of them underwent clean stereo- and regio-selective siloxymethylation.

碳链结构的转化和官能团的引入是有机合成的核心目的。该项目的目的是在给定有机分子的所需位置开发一种新的，有效的方法，并在扩展的碳链上同时形成新的功能组。为此，已经进行了有机分子与氢硅烷和一氧化碳的反应，并借助于过渡金属催化剂。重点是对反应条件的研究，因为存在在非常轻微的条件下（例如环境温度和压力）进行反应的可能性。在各种催化剂系统中，含有含有的复合物。发现钴是选择的催化剂。许多氧气和氮含有各种类型的化合物均经过催化反应系统，以表明某种含有反应性氧的化合物与水硅烷和一氧化碳反应。尤其是，环状醚在环境温度和压力下掺入一氧化碳的最佳结果。发现的净转换是硅氧基甲基环环开口，这是一个有用但非常困难的合成操作。许多具有多种替代模式的环状醚也受到催化系统的影响，其中大多数经历了干净的立体和区域选择性的硅氧甲基化。