2004 Fiscal Year Final Research Report Summary
Development of New Radical Coupling Reactions at Carbon-Heteroatom Multiple Bonds
| Project/Area Number |
14340229
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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 |
物質変換
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| Research Institution | Osaka City University (2003-2004)
Kyoto University (2002) |
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Principal Investigator |
YAMAGO Shigeru Osaka City University, Division of Molecular Material Science, Professor, 大学院・理学研究科, 教授 (30222368)
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| Project Period (FY) |
2002 – 2004
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| Keywords | Radical Reactions / Coupling Reactions / Combinatorial Chemistry / Multi-component Coupling Reactions / Silyltellurides / Tellurium / Silicon |
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| Research Abstract |
Radical mediated carbon-carbon bond formation at carbon-carbon multiple bonds, such as alkene and alkyne, has been widely utilized in organic synthesis due to its versatilities. However, little is known for the carbon-carbon bond formation at carbon-heteroatom multiple bonds, such as carbonyls and imines. This research was aimed to develop a new synthetic radical reaction at carbon-heteroatom multiple bonds based on the reaction of silyltellurides and carbon-heteroatom multiple bonds, which we have recently developed.
A new coupling reaction of carbonyl compounds with alkynes mediated by trimethylsilylphenyltelluride has been developed. The reaction proceeded under mild thermal conditions to give the corresponding E-allylic alcohols bearing vinyltelluride group with high stereoselectivity. Furthermore, radical- and anion-mediated transformations of the vinyltellurides were highly useful for the stereoselective synthesis of multi-substituted alkenes. Therefore, the coupling reaction followed by the transformations provides a powerful strategy for the synthesis of multi-substituted alkenes with defined geometry.
We have also developed a new coupling reaction of imines with isonitriles mediated by triethoxysilylphenyltelluride, a new class of silyltelluride reagent, to give α-silylaminomethylimidoyltellurides. The transformation of the carbon- tellurium bond in the coupling products afforded α-amino acid derivatives in good to excellent yields.
The above mentioned radical coupling reactions as well as the subsequent synthetic transformations are insensitive to the substitutions of carbonyls, imines, alkynes, and isonitriles. Therefore, we clarified that the current method is suitable for the combinatorial synthesis of small molecule libraries.
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[Journal Article] Highly Versatile Organostibine Mediators for Living Radical Polymerization2004
Author(s)
Yamago, S., Ray, B., Iida, K., Yoshida, J., Tada, T., Yoshizawa, K., Kwak, Y., Goto, A., Fukuda, T.
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Journal Title
J.Am.Chem.Soc. 126
Pages: 13908-13909
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Mechanism-Based Invention of High-Speed Living Radical Polymerization Using Organotellurium Compounds and Azo-Initiators2003
Author(s)
Goto, A., Kwak, Y., Fukuda, T., Yamago, S., Iida, K., Nakajima, M., Yoshida, J.
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Journal Title
J.Am.Chem.Soc. 125
Pages: 8720-8721
Description
「研究成果報告書概要(欧文)」より
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