| Project/Area Number |
11555241
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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 | 展開研究 |
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| Research Field |
Synthetic chemistry
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| Research Institution | The University of Tokyo |
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Principal Investigator |
KOBAYASHI Shu The University of Tokyo Graduate School of Pharmaceutical Sciences, Professor, 大学院・薬学・研究科, 教授 (50195781)
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| Co-Investigator(Kenkyū-buntansha) |
SAYOU Noboru TAKASAGO INTERNATIONAL CORPORATION, Research Institute of Fine & Aromachemicals, Chief (Researcher), ファイン&アロマケミカル研究所, 副部長(研究職)
YAMASHITA Yasuhiro The University of Tokyo Graduate School of Pharmaceutical Sciences, Assistant, 大学院・薬学・研究科, 助手 (90334341)
MANABE Kei The University of Tokyo Graduate School of Pharmaceutical Sciences, Lecturer, 大学院・薬学・研究科, 講師 (00251439)
石谷 暖郎 東京大学, 大学院・薬学系研究科, 助手 (50302617)
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| Project Period (FY) |
1999 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥13,900,000 (Direct Cost: ¥13,900,000)
Fiscal Year 2001: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 2000: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 1999: ¥8,300,000 (Direct Cost: ¥8,300,000)
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| Keywords | catalyst / asymmetric reaction / microencapsulated catalyst / osmium tetroxide / dihydroxylation / palladium / allylic alkylation / Suzuki coupling / マイクロカプセル化OsO_4 / MCOsO_4 / 二相系不斉ジヒドロキシル化反応 / マイクロカプセル化パラジウムトリフェニルホスフィン / アリル位置換反応 / クロスカップリング反応 / アレンルテニウム錯体 / オレフィンの閉環メタセシス / 高分子 / ジオール |
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| Research Abstract |
The utility of polymer catalysts is now well-recognized because of their ease of workup and of separation of products and catalysts, from the economical point of view, and in application to industrial processes, etc. However, in general, polymer catalysts have some disadvantages such as difficult preparation, instability, and low activity. To address these issues, we have already developed new types polymer catalysts, named 'microencapsulated catalysts,' which are readily prepared, have high activity, and are recoverable and reusable.
Catalytic asymmetric dihydroxylation of olefins using microencapsulated osmium tetroxide was developed. The catalyst was readily prepared from osmium tetroxide and an ABS polymer based on a microencapsulation technique. In most cases, the desired diols were obtained in high yields with high enantiomeric excesses.
We have also developed a phenoxyethoxymethylpolystyrene (PEM)-based novel polymer-supported osmium catalyst. The catalyst system does not require a slow addition of olefins, which has been a tedious procedure. The catalyst was recovered quantitatively by simple filtration and reused without loss of activity.
While palladium catalysts find wide-spread utility in a variety of transformations in organic synthesis, they are expensive, air-sensitive, and cannot be recovered in many cases. We have developed triphenylphosphine palladium, which has been successfully used in several palladium-catalyzed reactions.
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