Development of Oxymethylation Method Utilizing CO of Ambient Pressure

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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.