Design and Development of Room Temperature Carbonylation

本研究的目的是建立一个指导原则，开发催化系统，使室温羰基化。我们采取的策略是在分子催化剂中使用两个不同的金属中心，一个激活底物中的反应位点，另一个实现羰基化。因此，积累的知识导致建议使用硅钴作为催化剂的优势。例如，硅钴羰基配合物与含氧底物反应，劈开其碳-氧单键或双键，形成具有碳-钴键的中间体，后者是羰基化发生所必需的。随着这条线的发展，一些全新的含氧化合物如缩醛、内酯和芳香醛与一氧化碳和氢硅烷的催化反应被开发出来。这些新反应的立体化学方面已经得到澄清。期望这些结果将对设计新型催化剂体系和合成有机化学等领域做出重大贡献。

The objective of this research is to establish a guiding principle of developing catalytic systems that enable room temperature carbonylation. The strategy we took was to utilize two different metal centers in a molecular catalyst, one to activate a reaction site in a substrate, the other to effect carbonylation.Thus accumulated knowledge had lead to suggest the advantage of the use of silylcobalt as the catalyst for this purpose. For example, a silylcobalt carbonyl complex reacted with an oxygen-containing substrate and cleaved its carbon-oxygen single or double bond to result in the formation of an intermediate having a carbon-cobalt bond, the latter being essential for carbonylation to take place, Along with this line, a couple of entirely new catalytic reaction of oxygen-containing compounds such as acetals, lactones, and aromatic aldehydes with carbon monoxide and hydrosilanes have been developed. The stereochemical aspects of these new reactions have been clarified. It is expected that these results will make significant contribution to the fields of designing new catalyst system and synthetic organic chemistry.