1999 Fiscal Year Final Research Report Summary
Preparation of Planar Chiral Organometallics Having Ambiphilic Reactivity and Their Chemical Function
| Project/Area Number |
10650838
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
有機工業化学
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| Research Institution | Osaka Prefecture University |
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Principal Investigator |
NAKANISHI Saburo Engineering, Chemistry, Associate, 工学部, 助教授 (40081343)
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| Co-Investigator(Kenkyū-buntansha) |
TAKATA toshikazu Engineering, Chemistry, Professor, 工学部, 教授 (40179445)
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| Project Period (FY) |
1998 – 1999
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| Keywords | Allyliron complex / Planar Chirality / Carbonyl Complex / Nitrosyl complex / Asymmetric synthesis / Nucleophilic substitution |
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| Research Abstract |
1. Preparation of planar chiral (ηィイD13ィエD1-allyl)dicarbonylnitrosyliron complexes and the reactivity : Planar chiral ηィイD13ィエD1-allyldicabonylnitosyliron complexes were prepared by the reaction of optically active allyl tosylate and allyl bromide with tetrabutylammonium tricarbonyl nitrosylferrate (TBAFe). The optical purity and planar chinrality of the complexes thus obtained depended on reaction solvent and leaving group of the allylic substrates. Amines reacted regioselectively with (ηィイD13ィエD1-allyl)dicarbonylnitrosyliron complexes thus obtained to give γ-amino α,β-unsaturated esters in high yields.
2.Preparation of (ηィイD13ィエD1-allyl)dicarbonylnitrosyliron complexes via transmetallation of (ηィイD13ィエD1-allyl)palladium complexes : Treatment of (ηィイD13ィエD1-allyl)bronmopalladium complexes with TBAFe afforded (ηィイD13ィエD1-allyl)discarbonyl-nitrosyliron conplexes in good yields. The highest yield of the (ηィイD13ィエD1-allyl)dicarbonylnitrosyliron complex was obtained from the reaction in dic
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hloromethane at -20℃. The reaction provides a new route to (ηィイD13ィエD1-allyl)dicarbonylnitrosyliron complexes by transmetallation of the ηィイD13ィエD1-allyl ligand from palladium to iron metal.
3. Formation of (ηィイD13ィエD1-1-azzallyl)dicarbonylnitrosyliron Complexes : Preparation of (ηィイD13ィエD1-1-azaallyl)dicarbonylnitrosyliron complexs was achieved by the reaction of α-bromo-N-methoxyalkanimines with TBAFe at 0〜40℃. Reaction of two equivalents of α-bromo-N-methoxyalkanimines with the ferrate at a temperature above 40℃ resulted in reductive dimerization of α-bromoimines via (ηィイD13ィエD1-1-azaallyl)dicarbonylnitrosyliron complex.
4. A Route to Functionalized (ηィイD13ィエD1-Allyl)dicarbonylnitrosyliron Complexes : (ηィイD13ィエD1-2-Acylallyl)-dicarbonylnitrosyliron Complexes via Regio- and Stereoselective Acylmetallation of Allences : Reaction of allenes with alkyl halides in the presence of TBAFe proceeds regio- and stereoselectively to give anti-(ηィイD13ィエD1-allyl)dicarbonylnitrosyliron complexes bearing acyl group at central carbon of the allyl ligand in good yields. The reaction provides a facile synthesis of di- and trisubstituted ηィイD13ィエD1-allyl iron complexes with acyl group via acylation of the central carbon of the allenes. Less
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Research Products
(10 results)
