Development of Oxymethylation Method Utilizing CO of Ambient Pressure

碳链结构的转化和官能团的引入是有机合成的中心目标。本项目的目标是开发一种新的、有效的方法，在给定的有机分子的理想位置上延伸一条碳链，同时在延伸的碳链上形成新的官能团。为此，我们研究了有机分子与氢硅烷和一氧化碳在过渡金属催化剂作用下的反应。重点研究了反应条件，因为有可能在非常温和的条件下进行反应，如常温和常压。钴已被发现是催化剂的首选。许多不同类型的含氧和含氮化合物被用于催化反应系统，结果表明，某些含氧化合物与氢硅烷和一氧化碳反应。特别是，环醚在常温常压下加入一氧化碳的效果最好。发现的净转化是硅氧甲基开环，这是一种有用的合成操作，但在其他方面非常困难。许多具有不同取代模式的环醚也被催化体系催化，其中大多数经历了干净的立体和区域选择性硅氧甲基化。

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.