Development of Practical Catalysts by an Efficient Integration of A Dynamic Bifunctional Catalyst and Supercritical Fluid Chemistry

通过概念上的新的双功能催化剂和独特的反应介质超临界流体的组合，已经开发出高效的催化反应过程。用于不对称C-C键形成的手性双功能分子催化剂的发展：一种概念上的新型手性双功能过渡金属基分子催化剂被开发出来促进不对称C-C键的形成。与手性酰胺络合物的不对称Nicahel反应顺利地进行，得到了相应的高原子经济性和高ee的手性加合物。目前的双功能分子催化剂为立体选择性转化提供了新的基础，包括对映体选择性的C-H和C-C以及C-N和C-O键的形成。2-甲基氮杂环丙烷与超临界二氧化碳制备的脂肪族聚氨基甲酸酯-胺共聚物的双刺激响应行为：在Superc…下氮杂环丙烷与二氧化碳的反应更临界的条件，以得到含有氨基甲酸酯和胺部分的无规共聚物。由2-甲基氮杂环丁烷和二氧化碳得到的共聚产物在温度和pH的响应下都表现出急剧和快速的相变。超临界状态下的反应条件可以控制其响应性。多功能固体催化剂上官能化化合物与超临界甲醇的连续化学选择甲基化：利用连续流动固定床反应器，成功地实现了酚类和乙醇胺与超临界甲醇在金属氧化物催化剂上的化学选择甲基化反应。苯酚在双功能催化剂Cs-P-Si上的甲基化反应具有很弱的酸性和碱性，选择性地产生0-甲基化产物，而较弱的酸碱双功能催化剂ZrO_2主要提供C-甲基化产物。同时，氨基醇在Cs-P-Si混合氧化物上的甲基化反应优先产生N-甲基化产物。超临界条件下固体催化剂的酸碱性质和超临界流体的性质对反应的化学选择性有很大影响。较少

Highly efficient catalytic reaction processes have been developed by a combination of the conceptually new bifunctional catalysts and unique reaction media, supercritical fluids.1. Development of Chiral Bifunctional Molecular Catalysts for Asymmetric C-C Bond Formation : A conceptually new chiral bifunctional transition metal-based molecular catalyst promoted the enantioselective C-C bond formation has been developed. Asymmetric Nicahel reactions with chiral amide complexes proceeds smoothly to give the corresponding chiral adducts with high atom economy and high ee. The present bifunctional molecular catalyst offers a great opportunity to open up new fundamentals for stereoselective transformation including enantioselective C-H and C-C as well as C-N and C-0 bond formation.2. Double Stimuli-Responsive Behavior of Aliphatic Poly(urethane-amine) Copolymers Prepared from 2-Methylaziridine and Supercritical Carbon Dioxide : A reaction of aziridines and carbon dioxide proceeds under superc … More ritical conditions to give random copolymers containing urethane and amine moieties. The resulting copolymeric products obtained from 2-methylaziridine and carbon dioxide exhibit sharp and rapid phase transitions in response to both temperature and pH. The responsive property can be controlled by the reaction conditions under supercritical state.3. Continuous Chemoselective Methylation of Functionalized compounds with Supercritical Methanol over Mulitifunctionalized Solid Catalysts : The chemoselective methylation of phenols and ethanol amine with supercritical methanol over the metal oxide catalysts has been successfully developed using a continuous flow fixed bed reactor. Methylation of phenols over the bifunctional catalyst, Cs-P-Si, having both very weak acidic and basic sites, gives selectively the 0-methylation products, while the weaker acid-base bifunctional catalyst ZrO_2 provids mainly C-methylation products. Whilst, the methylation of aminoalcohols over the Cs-P-Si mixed oxide produces preferentially N-methylated products. The chemoselective outcome of the reaction is highly influenced by the acid-base character on the solid catalysts under supercritical conditions and the nature of the supercritical fluids. Less