2006 Fiscal Year Final Research Report Summary
Development of Practical Catalysts by an Efficient Integration of A Dynamic Bifunctional Catalyst and Supercritical Fluid Chemistry
| Project/Area Number |
14078209
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
IKARIYA Takako Graduate School of Science and Engineering, Professor, 大学院理工学研究科, 教授 (30107552)
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| Project Period (FY) |
2002 – 2005
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| Keywords | Asymmetric catalysis / Synthetic Chemistry for fine chemicals / Catalysis-Chemical process / Reduction of carbon dioxide emissions / Chemistry of Supercritical Fluids / Multi-functional catalysts |
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| Research Abstract |
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
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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
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