| Project/Area Number |
07454163
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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 |
Organic chemistry
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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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| Project Period (FY) |
1995 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥7,700,000 (Direct Cost: ¥7,700,000)
Fiscal Year 1996: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1995: ¥5,200,000 (Direct Cost: ¥5,200,000)
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| Keywords | Catalytic Asymmetric Synthesis / Attractive Interactions / Chiral Monophosphines / Chiral Ferrocenylphosphines / Chiral Bisoxazolines / Asymmetric Oxidation / Asymmetric Substitutions / 光学活性単座配位子 / ワッカー型反応 / MOP配位子 / 軸不斉ビナフチル / 光学活性ビスオキサゾリン / boxax配位子 / 不斉ヒドロシリル化 |
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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 enantioselectivity as well as in catalytic activity. In designing chiral ligands we have attached importance to introduction of a functional group into the ligand that, where possible, would be expected to interact attractively with a functional group in the substrate. The attractive interactions will enhance the enantioselectivity in catalytic asymmetric reactions by increased steric interactions between the chiral ligand and a prochiral substrate. We have developed new chiral ligands bearing some functional groups on the backbone : 1) 2- (Diphenylphosphino) -1,1'-binaphthyls (MOPs) which have carboxyl, hydroxy, alkoxy, and amino groups on the 2'-position. 2) Ferrocenyl-and ruthenocenylbisphosphines containing amino and hydroxy groups on the metallocene side chain. 3) Several kinds of functional groups were introduced into 3-and 3'-positions of 2,2'-bis [4- (alkyl) oxazol-2-yl] -1,1'-binaphthyls (boxax). These functionalized chiral ligands have been used for palladium-catalyzed asymmetric reactions including allylic substitutions and Wacker-type cyclization.
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