2004 Fiscal Year Final Research Report Summary
Generation of Transition Metal-Containing 1,3-Dipoles and their Application for the Synthesis of Cyclic Compounds
| Project/Area Number |
14340194
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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 | Tokyo Institute of Technology |
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Principal Investigator |
KUSAMA Hiroyuki Tokyo Institute of Technology, Department of Chemistry, Associate Professor, 大学院・理工学研究科, 助教授 (30242100)
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| Project Period (FY) |
2002 – 2004
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| Keywords | Tungsten / 1,3-Dipolar / Cycloaddition / carbene Complex / Indole |
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| Research Abstract |
In this research project, generation of transition metal-containing 1,3-dipoles, novel reactive species, and their application for the synthesis of polycyclic compounds were investigated. When the o-alkynylphenyl carbonyl derivatives were treated with a catalytic amount of W(CO)5(thf), 6-endo-mode of cyclization of the carbonyl oxygen onto the electrophilically-activated alkyne moiety took place to give novel reactive species, tungsten-containing carbonyl ylides, which reacted with electron-rich alkenes to give oxygen-containing polycyclic compounds through [3+2]-cycloaddition reaction followed by intramolecular C-H insertion of the produced non-stabilized carbene complex intermediates. In the presence of triethylsilane, these tungsten-containing carbene intermediates were smoothly trapped intermolecularly by triethylsilane to give silicon-containing cycloadducts with regeneration of the W(CO)5 species.
Similarly, treatment of N-(o-alkynylphenyl)imine derivatives with W(CO)5(L) induces the 5-endo-mode of cyclization of the imine nitrogen onto the electrophilically-activated alkyne moiety to afford metal-containing azomethine ylides. [3+2]-cycloaddition of these ylide species with various electron-rich alkenes also proceeded smoothly to give unstable carbene complexes, which in turn undergo 1,2-hydrogen, alkyl, aryl-migration to afford in good yield 6-5-5 tricyclic indole skeletons having an alkyl or an aryl substituent at the 3-position of indole nucleus.
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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-Butyl-dimethylsiloxy-alk-2-enylsulfonium Salt 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
Description
「研究成果報告書概要(欧文)」より
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