| Project/Area Number |
04453147
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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 |
Chemical pharmacy
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| Research Institution | Hokkaido University |
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Principal Investigator |
HAYASHI Tamio Catalyziz Research Center Hokkaido University, Professor, 触媒化学研究センター, 教授 (00093295)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1993: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1992: ¥4,700,000 (Direct Cost: ¥4,700,000)
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| Keywords | Catalytic Asymmetric Synthesis / Transition Metal Catalyst / Asynmmetric Displylation / Chiral Phosphhine Ligands / Asymmetric Hydrosilylation / Asymmetric Aldol Reaction / Asymmetric Coupling / パラジウム / 光学活性配位子 / ヒドロホウ素化 / アレニルボラン / 1,3ーエンイン |
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| Research Abstract |
Asymmetric reactions catalyzed by transition metal complexes containing optically active phosphine ligands have attracted significant interest for their synthetic utility. One of the most exciting and challenging subjects in research on the catalytic asymmetric synthesis is development of the chiral ligand which will fit in with a given reaction efficientlyin catalytic activity as well as in enantioselectivity. We have dveloped several types of new chiral phosphine ligands represented by 2-(diphenylphosphino)-2'-alkoxy-1, 1'-binaphthyls (MOPs). The axially chiral monodentate phosphine ligands MOPs were found to be efficient ligands for three types of new palladium-catalyzed asymmetric reactions : 1) Asynmmetric hydrosilylation of olefins which provides a new efficient route to optically active alcohols. 2) Asynmmetric hydroboration of 1, 3-enynes giving optically active allenylboranes. 3) Asynmmetric reduction of allylic esters with formic acid.
We have also carried out mechanistic studies on palladium-catalyzed asymmetric Heck type reaction, asymmetric silylation of allylic chlorides, and asymmetric aldol reAction of isocyanoacetate with fluorinated benzaldehydes in the presence of chiral ferrocenylphosphine-gold(I) catalyst.
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