Development of Synthetic Methods for the Silaallene Cationic Species and the Related Compounds and Their Application Reactions
| Project/Area Number |
16390008
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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 |
Chemical pharmacy
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| Research Institution | The University of Tokushima |
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Principal Investigator |
NAGAO Yoshimitsu The University of Tokushima, Graduate School, Institute of Health Biosciences, Professor, 大学院ヘルスバイオサイエンス研究部, 教授 (40027074)
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| Co-Investigator(Kenkyū-buntansha) |
SANO Shigeki The University of Tokushima, Graduate School, Institute of Health Biosciences, Associate Professor, 大学院ヘルスバイオサイエンス研究部, 助教授 (20226038)
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| Project Period (FY) |
2004 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥14,500,000 (Direct Cost: ¥14,500,000)
Fiscal Year 2006: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2005: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 2004: ¥7,700,000 (Direct Cost: ¥7,700,000)
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| Keywords | silaallene / diarylmonoalkynylfluorosilane / dialkynyldiarylsilane / oxasiletane / azasiletane / silacyclobutene / desilylation / conjugated diene / シラレン / シラアレンカチオン / ジアリルアルキニルフルオロシラン / ジアリルジアルキニルシラン / テトラクロロシラン / ジアリルジフルオロシラン / X線結晶構造解析 / テトラフルオロシラン / アリルトリクロロシラン / ジアリルジクロロシラン |
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| Research Abstract |
First, we have developed highly efficient synthetic methods for diarylmonoalkynylfluorosilanes and dialkynyldiarylsilanes as follows. Reaction of aryllithiums with tetrachlorosilane gave monoaryltrichlorosilanes, which were treated with other aryllithiums to afford diaryldichlorosilanes. After halogen exchange reaction (Cl→F), treatment of the resulting diaryldifluorosilanes with alkynyllithiums gave the desired diarylmonoalkynylfluorosilanes. Their similar reactions with other alkynyllithiums furnished the corresponding alkynyl-substituted dialkynyldiarylsilanes in excellent yields. Treatment of the monoalkynylmonoarylfluorosilane bearing t-Bu, Tip, phenylalkynyl, and fluorine atom with t-BuLi at 0℃ and then at room temperature or under reflux generated a 1-silaallene. The 1-silaallene was in situ allowed to react with ketones, aldehydes, and an imine to give the corresponding 1,2-oxasiletanes and 1,2-azasiletane, respectively. Treatment of the differrent kinds of alkynyl-substituted dialkynyldiarylsilanes with biscyclopentadienylzirconocene-ethylene complex followed by acidification with 3N HC1 gave regio-and stereoselectively the corresponding silacyclobutenes in good yields. Desilylation of the silacyclobutenes with tetrabutylammonium fluoride afforded stereoselectively unsymmetrical conjugated dienes and trienes in excellent yields, respectively.
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Report
(4 results)
Research Products
(17 results)
