2005 Fiscal Year Final Research Report Summary
Generation and Reaction of Multi-functionalized Transition Metal Reactive Species
| Project/Area Number |
15205006
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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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 | Tokyo Institute of Technology |
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Principal Investigator |
IWASAWA Nobuharu Tokyo Institute of Technology, Department of Chemistry, Professor, 大学院・理工学研究科, 教授 (40168563)
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| Project Period (FY) |
2003 – 2005
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| Keywords | Metal-Containing Carbonyl Ylide / Matal-Containing Azomethine Ylide / Tungsten Carbonyl / [3+2] Cycloaddition Reaction / Carbene Complex / Electrophilic Activation of Alkynes / Geminal Carbo-functionalization / Rhenium Carbonyl |
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| Research Abstract |
In this research, generation and reaction of novel multi-functional reactive species are studied extensively. It is expected that electiophilic activation of alkynes with W(CO)_5(L) followed by attack of nucleophiles on them would give novel multi-functional reactive species, which are expected to behave both as a 1,3-dipole and as a carbene complex. Based on this concept, several unique and synthetically useful reactions have been developed.
In the first place, generation and reaction of novel tungsten-containing carbonyl and azomethine ylides were developed. Treatment of ο-ethynylphenyl ketones or N-(ο-alkynylphenyl)imine derivatives with W(CO)_5(thf) generated the tungsten-containing 1,3-dipoles by the endo-mode of attack of the carbonyl oxygen or imino nitrogen onto the electrophilically activated alkyne moiety. The [3+2]-cycloaddition of the generated ylides with electron-rich alkenes followed by insertion of the resulting tungsten carbene moiety into a neighboring C-H bond or 1,2-
… More
alkyl-migration realized the construction of complex cyclic carbon frameworks in a single step. This reaction proceeded even with a catalytic amount of W(CO)_5(thf). Thus, novel multi-functional reactive species are successfully generated and react with alkenes to give synthetically useful compounds in a single operation.
We next examined the possibility of realizing geminal carbo-functionalization of alkynes. Treatment of ω-acetylenic dienol silyl ethers with W(CO)_6 under photoirradiation gave bicyclo[3.3.0]octane derivatives, which were produced by addition of the silyl enol ether to the electrophilically activated alkynes to give alkenylmetallic intermediates. This further reacted with α,β-unsaturated oxonium moiety at the position β to the metal to give carbene complex intermediates, which underwent typical carbene reactions to give the products. This method constitutes a catalytic method for the geminal carbo-functionalization of alkynes. ReCl(CO)_5 showed paiticularly high activity for this reaction ; even 0.5〜3.0 mol% of ReCl(CO)_5 were sufficient to promote the reaction efficiently. Less
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Research Products
(32 results)
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[Journal Article] Indium-Mediated β-Allylation, β-Propargylation, and β-Allenylation onto α,β-Unsaturated Ketones : Reactions of in-Situ-Generated 3-tert-Butyldimethylsillyloxyalk-2-enylsulfonium Salts with in-Situ-Generated Organoindium Reagents2003
Author(s)
K.Lee, H.Kim, T.Miura, K.Kiyota, H.Kusama, S.Kim, N.Iwasawa, P.H.Lee
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Journal Title
J.Am.Chem.Soc. 125
Pages: 9682-9688
Description
「研究成果報告書概要(欧文)」より
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