| Project/Area Number |
06557116
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| Research Category |
Grant-in-Aid for Developmental 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 | Kyoto University |
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Principal Investigator |
HAYASHI Tamio Kyoto University, Department of Chemistry Professor, 大学院・理学研究科, 教授 (00093295)
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| Co-Investigator(Kenkyū-buntansha) |
SAYO Noboru Takasago International Corp., Research Lab.Assist.Manager, 研究主管
KUMOBAYASHI Hidenori Takasago International Corp., Research Lab.Director, 所長
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| Project Period (FY) |
1994 – 1995
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| Project Status |
Completed (Fiscal Year 1995)
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| Budget Amount *help |
¥7,600,000 (Direct Cost: ¥7,600,000)
Fiscal Year 1995: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1994: ¥6,000,000 (Direct Cost: ¥6,000,000)
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| Keywords | Catalytic Asymmetric Synthesis / Chiral Monodentate Ligands / Asymmetric Hydrosilylation / MOP Ligands / Axially Chiral Binaphthyls |
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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 efficiently in catalytic activity as well as in enantioselectivity. We have developed new monodentate phosphine ligands represented by 2- (diphenylphosphino) -2'-methoxy-1,1'-binaphthyl (MeO-MOP), whose chirality is due to the binaphthyl axial chirality. The axially chiral monophosphine ligands MOPs were found to be very efficient for three types of new palladium-catalyzed asymmetric reactions : 1) Asymmetric hydrosilylation of olefins which provides a new efficient route to optically active alcohols. 2) Asymmetric hydroboration of 1,3-enynes giving optically active allenylboranes. 3) Asymmetric reduction of allylic esters with formic acid. We have elucidated the preparation methods for MOP ligands in a large scale starting with optically active 2,2'bis (hydroxy) -1,1'-binaphthyl. Preparation of new MOP derivatives bearing several substituents at 2'-position were also achieved by use of palladium-or nickel-catalyzed cross-coupling type reactions.
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