1999 Fiscal Year Final Research Report Summary
Development of 5 Components Coupling Reaction of Dienes
| Project/Area Number |
10650860
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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 |
Synthetic chemistry
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| Research Institution | Osaka Prefectural College of Technology |
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Principal Investigator |
ITOH Keiji Osaka prefectural College of Technology, Professor, 工業化学科, 教授 (10241225)
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| Co-Investigator(Kenkyū-buntansha) |
NAKANISHI Saburo Department of Applied Chemistry, Osaka Prefecture University, Assistant Professor, 工学部, 助教授 (40081343)
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| Project Period (FY) |
1998 – 1999
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| Keywords | π-ally1 complex / nitorosyliron complex / double carbonylation / acylmetallation / 1,3-butadiene / allene |
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| Research Abstract |
In this study, the aim is development of 5 components coupling reaction. That is, in the presence of alkyl halides and tricarbonylnitrosylferrate, acylmetallation of 1,3-butaienes or 1,2-dienes was discussed and the carbonyl insertion reaction of the resulting iron complexes with 1,2-bis(diphenylphosphino)ethane (DPPE) following the alcoholysis with ethanol was discussed. In the result, the coupling reaction of 5 components of 1,2-dienes or 1,3-butadienes, two molecules of carbon monoxide from tricarbonylnitrosylferrate, alkyl halides, and ethanol completes stereo- and regioselectively.
In the presence of tetrabutylammmonium tricarbonylnitrosylferrate (TBAFe), 1,2-dienes (allenes) and alkyl halides reacted to give (η^3-2-acylally1) dicarbonylnitrosyliron complexes accompanied with acylmetallation of allenes in good yields.
In the presence of TBAFe, 1,3-butadienes and alky1 halides reacted to give (η^3-1-acylmethylally1) dicarbonylnitrosyliron complexes accompanied with acylmetallation of 1,3-butadienes in good yields. The resulting iron complexes reacted with DPPE at the less hindered site of the allylic ligand to give ε-acy1-β, γ-unsaturated acyliron complexes. In succession, the alcoholysis of the acyliron complexes with ethanol gave the corresponding ε-acy1-β, γ-unsaturated carboxylic esters. In a similar manner, (η^3-2-acylally1) dicarbony1-nitrosyliron complexes obtained from 1,2-dienes (allenes) and alky1 halides with TBAFe gave the β-acy1-β, γ-unsaturated acyliron complexes followed by alcoholysis with ethanol to give the β-acy1-β, γ-unsaturated carboxylic esters.
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