2007 Fiscal Year Final Research Report Summary
Creation and Systematization of New Organic Cation Chemistry
| Project/Area Number |
17205012
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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 |
Synthetic chemistry
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| Research Institution | Kyoto University |
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Principal Investigator |
YOSHIDA Jun-ichi Kyoto University, Graduate School of Engineering, Professor (30127170)
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| Co-Investigator(Kenkyū-buntansha) |
NOKAMI Toshiki Kyoto University, Graduate School of Engineering, Assistant Professor (60402963)
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| Project Period (FY) |
2005 – 2007
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| Keywords | organic cations / cation pool method / reactivity / stability / N-acyliminium ions / alkoxycarbenium ions / diarylcarbenium ions / cationic organosulfur compounds |
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| Research Abstract |
The present study was aimed at deepening the chemistry of organic cations using the cation pool method, which involved the generation and accumulation of organic cations by low temperature electrochemical oxidation of organic compounds in the absence of nucleophiles. The stability and reactivity of the organic cations such as N-acyliminium ions and alkoxycarbenium ions were studied, and several reactions were newly designed and developed.
1. Structures and stability of organic cations
NMR studies on organic cations were carried out based on the cation pool method. The relationship between thermal stability and cation structures was also studied.
2. Synthetic applications of organic cations.
Various organic cations were generated by the cation pool method and used for synthetic reactions. For example, diarylcarbenium ion pools were generated by the oxidative C-H bond dissociation of diarylmethanes using anodic oxidation. ArS (ArSSAr) + was generated electrochemically from ArSSAr and was used for the synthesis of organosulfur compounds. In addition, a sequential one-pot indirect method for the generation of alkoxycarbenium ion pools was developed using the reaction of ArS (ArSSAr) + with a thioacetal. An ArS (ArSSAr) +-initiated chain reaction involving intramolecular carbon-carbon bond formation was also developed. And furthermore, coupling of an N-acyliminium ion pool with a benzylsilane, which proceeded by a chain mechanism involving oxidative C-Si bond cleavage, was developed.
The results obtained in the present research add a new dimension of the chemistry of organic cations.
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[Journal Article] Electrochemical Generarion of Glycosyl Triflate Pools2007
Author(s)
T., Nokami, A., Shibuya,H., Tsuyama, S., Suga, A.A., Bower, D., Crich, J., Yoshida
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Journal Title
J. Am. Chem. Soc 129
Pages: 10922-10928
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Generation of pyridyl coordinated organosilicon cation pool k oxidative Si-Si bond dissociation2007
Author(s)
T., Nokami, R., Soma, Y., Yamamoto, T., Kamei, K., Itami, J., Yoshida
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Journal Title
Beilstein J Org. Chem
Pages: 3-7
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Control of Extremely Fast Competitive Consecutive Reactions Control Using Micromixing. Selective Friedel-Crafts Aminoalkylation2005
Author(s)
A., Nagaki, M., Togai, S., Suga, N., Aoki, K., Mae, J., Yoshida
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Journal Title
J. Am. Chem. Soc 127
Pages: 11666-11675
Description
「研究成果報告書概要(欧文)」より
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