| Project/Area Number |
12305057
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
IKARIYA Takao Graduate school of science and Engineering, professor, 大学院・理工学研究科, 教授 (30107552)
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| Co-Investigator(Kenkyū-buntansha) |
ITO Masato Graduate school of science and Engineering, Research Assistant, 大学院・理工学研究科, 助手 (20293037)
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| Project Period (FY) |
2000 – 2002
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| Project Status |
Completed (Fiscal Year 2002)
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| Budget Amount *help |
¥32,200,000 (Direct Cost: ¥27,700,000、Indirect Cost: ¥4,500,000)
Fiscal Year 2002: ¥9,750,000 (Direct Cost: ¥7,500,000、Indirect Cost: ¥2,250,000)
Fiscal Year 2001: ¥9,750,000 (Direct Cost: ¥7,500,000、Indirect Cost: ¥2,250,000)
Fiscal Year 2000: ¥12,700,000 (Direct Cost: ¥12,700,000)
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| Keywords | molecular catalyst / metal amide complex / acid-base cooperative effect / dynamic function / C-H bond activation / transfer hydrogenation / supercritical fluid / C-C bond formation / 金属ヒドリド錯体 / 二酸化炭素挿入反応 / 不斉クラスター触媒反応 / CH結合活性化 / 光学活性ジオール / 炭素炭素結合形成反応 |
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| Research Abstract |
A well-defined chiral transition metal amide complex with a M/NH bifunctional unit, Ru(Tsdpen)η^6-arene) or C_p^*M(Tsdpen), (M = Rh, Ir), has sufficient Bronsted basicity to deprotonate 2-propanol or formic acid and acidic organic compounds, leading to a hydrido amine complex and amine complexes bearing a metal bonded C- nucleophile, respectively. Thanks to a rapid and effective interconversion between the amide complex and the amine complex, the chiral amide complex has proven to effect asymmetric transfer hydrogenation of α-substituted aromatic ketones and asymmetric Michael addition to cyclic eneones in a highly stereoselctive manner. The dynamic M/NH bifunctional effect can be applied to the chiral Ru cluster-based catalyst systems generated in situ from Ru_3(CO)_<12> and chiral diiminodiphosphine tetradentate ligands. This chiral cluster effected asymmetric transfer hydrogenation of aromatic ketones in 2-propanol, leading to optically active alcohols with high ee. The dynamic mult
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i-functional effect of both the amide and the amine complexes is responsible for the excellent catalyst performance in terms of high reactivity, selectivity, and practicability.
We have demonstrated that supercritical fluids are promising reaction media for molecular catalysis and the utilization of a particular fluid, scCO_2 caused a remarkable enhancement of reactivities and selectivities of molecular catalysts. In order to gain deeper understanding of the reaction mechanism of the molecular catalysis in this unique media, a supercritical fluid nuclear magnetic resonance (scNMR) spectroscopic method has been developed using a commercially available NMR spectrometer equipped with a high-pressure zirconia cell. We found that trialkylphosphite ligands are highly effective for increasing the solubility of dichloropalladium(II) and dichlororuthenium(II) complexes in scCO_2 and the Ru complex promoted rapid vinyl carbamate formation from phenylacetylene, diethylamine, and scCO_2. The scNMR investigation on a dynamic behavior of diethylamine in scCO_2 revealed that formation of N, N-diethylcarbamic acid was reversible and the concentration of the carbamic acid was highly influenced by the pressure and temperature. Less
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