Development of Benign Chemical Processes on Nano-seized Reaction Environments

从环境的观点来看，开发没有有害废物的高效化学过程是一个重要的课题。在我们的项目中，开发在水中的有机反应和开发聚合物固定化催化剂已被集中。主要研究结果如下：1.水中有机反应是环境友好化学过程中最有前途的方法之一。此外，水有时对有机反应的反应性和选择性起着有趣的作用。对水中有机反应进行了研究，发现Brφnsted酸-表面活性剂复合催化剂通过形成疏水反应环境，对水中脱水反应起到良好的反应促进作用。我们还发现聚合物支载Brφnsted酸在水介质中的脱水反应、醇的脱保护反应等反应中是有效的。此外，在水介质中还实现了高对映选择性的Mannich型反应和羟甲基化反应。2.高官能化的有机金属催化剂有时会对人体和环境造成危害。因此，重要的是开发没有任何有机金属废物的化学工艺。我们的小组已经开发出了微胶囊方法来固定含金属的催化剂。在这个项目中，我们专注于有用的含金属催化剂，钌，钯和锇化合物的固定化。这些试剂被成功地固定在新型聚合物上，具有完美的回收和重复使用。这些催化剂也可用于烯烃的复分解、加氢和不对称二羟基化反应。所获得的结果将有助于开发清洁的化学过程。

Development of highly efficient chemical processes with no harmful waste is an important subject from an environmental viewpoint. In our project, development of organic reactions in water and development of polymer-immobilized catalysts have been focused. The results obtained are summarized below.1.Organic reaction in water is one of the most promising methods in environmental benign chemical processes. Furthermore, water sometimes plays an interesting role on reactivity and selectivity of organic reactions. We carried out investigations of organic reactions in water, and it was found that a Brφnsted acid-surfactant combined catalyst worked as a good reaction promoter in dehydrating reactions in water by forming hydrophobic reaction environments. We also showed that polymer supported Brφnsted acid is effective in several reactions in water ; for example, dehydrating reactions, deprotecting reactions of alcohols, etc. Moreover, highly enantioselective Mannich-type reactions and hydroxymethylation in aqueous media were also achieved. Those results would inspire that water is a promising solvent.2.Highly functionalized organometallic catalysts were sometimes harmful to human body and environment. Therefore, it is important to develop chemical processes without any organometallic waste. Our group has already developed microencapsulate methods for immobilizing metal-containing catalysts. In this project, we focused immobilization of useful metal-containing catalysts, ruthenium, palladium and osmium compounds. Those reagents were successfully immobilized on novel polymers with perfect recovery and reuse. Those catalysts were also employed in metathesis, hydrogenation, and asymmetric dihydroxylation of olefins with high efficiency. The results obtained would contribute to development of clean chemical processes.