| Project/Area Number |
02453089
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Hokkaido University |
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Principal Investigator |
HAYASHI Tamio Hokkaido University, Catalysis Research Center, Professor, 触媒化学研究センター, 教授 (00093295)
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| Co-Investigator(Kenkyū-buntansha) |
MATSUMOTO Yonetatsu Hokkaido University, Catelysis Research Center, Research Assosiate, 触媒化学研究センター, 助手 (60219524)
OZAWA Fumiyuki Hokkaido University, Catelysis Research Center, Associate Professor, 触媒化学研究センター, 助教授 (40134837)
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| Project Period (FY) |
1990 – 1991
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| Project Status |
Completed (Fiscal Year 1991)
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| Budget Amount *help |
¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 1991: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1990: ¥4,300,000 (Direct Cost: ¥4,300,000)
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| Keywords | Catalytic Asymmetric Synthesis / Transition Metal Catalyst / Optically Active Compounds / Asymmetric Heck Reaction / Asymmetric Hydrosilylation / Asymmetric Hydroboration / Asymmetric Aldol Reaction / Asymmetric Allylation |
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| Research Abstract |
1. A highly enantioselective arylation of olefins (asymmetric Heck reaction) was achieved by using aryl triflates as arylating reagents and a chiral palladium catalyst. (1) The reaction of 2, 3-dihydrofuran in the presence of 1, 8-bis (dimethylamino) naphthalene as a base gave 2-aryl-2, 3-dihydrofurans of 87-96% ee. (2) The reaction of N-substituted 2-pyrrolines gave 2-aryl-5-pyrrolines of up to 83% ee.
2. Novel catalytic asymmetric reactions were developed by using a newly designed chiral monophosphine ligand (MOP). (1) Asymmetric hydrosilylation of 1-alkenes in the presence of a Pd-MOP catalyst gave optically active 2-silylalkanes, which were easily converted into 2-alkanols of 94-97% ee. (2) Catalytic asymmetric hydroboration of 1, 3-enynes gave optically active allenylboranes of up to 60% ee. (3) Optically active 3, 7-dimethylocta-1, 6-diene (70% ee) was prepared by reductive cleavage of geranyl acetate with formic acid in the presence of a Pd-MOP catalyst.
3. A series of chiral ferrocenylbisphosphines containing an aminoalkyl side chain were prepared and their efficiency as a chiral ligand in the Au (I)- or Ag (I)-catalyzed asymmetric aldol reaction of isocyanoacetate was examined.
4. Asymmetric double hydroboration of 1, 3-diene was performed with chiral phosphine-rhodium complexes.
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