| Project/Area Number |
18350048
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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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 | The University of Tokyo |
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Principal Investigator |
NISHIBAYASHI Yoshiaki The University of Tokyo, Graduate School of Engineering, Associate Professor (40282579)
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| Co-Investigator(Kenkyū-buntansha) |
MIYAKE Yoshihiro The University of Tokyo, Graduate School of Engineering, Associate Professor (00347270)
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| Project Period (FY) |
2006 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥16,130,000 (Direct Cost: ¥14,900,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2007: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2006: ¥10,800,000 (Direct Cost: ¥10,800,000)
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| Keywords | Catalytic Reactions / Ruthenium / Substitution Reactions / Sulfur / Asymmetric Synthesis / Chiral Lieands / Enantioselectivit / Polynuclear complexes |
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| Research Abstract |
We have developed novel transformations only promoted by polynuclear transition metal complexes such as heteroatom-bridged diruthenium complexes. We have newly found the following three topics. (1) We have found enantioselective propargylation of aromatic compounds such as N,N-dimethylanilines, 2-methylfuran, and N-substituted indoles with propargylic alcohols catalyzed by thiolated-bridged diruthenium complexes bearing optically active thiolate ligands to give the corresponding propargylated aromatic compounds in good to high yields with a high enantioselectivity (up to 94% ee). (2) We have found novel reactions between propargylic alcohols and acetone catalyzed by dicationic chalcogenolated-bridged diruthenium complexes to give the corresponding hexadienones in moderate to good yields, in sharp contrast to the formation of γ-ketoalkynes when neutral or monocationic diruthenium complexes are employed as catalysts. (3) We have newly prepared phosphido-bridged diruthenium complexes and investigated their catalytic activity toward reactions of propargylic alcohols with aromatic compounds to give the corresponding α,β-unsaturated ketones in moderate yields. In addition, we have developed novel some reactions catalyzed by thiolate-bridged diruthenium complexes such as vinylic substitution reactions with nucleophiles via butatrienylidene complexes as key intermediates.
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