| Project/Area Number |
03453100
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Nagoya University |
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Principal Investigator |
YAMAMOTO Hisashi Nagoya University, Faculty of Engineering, Professor, 工学部, 教授 (10135311)
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| Co-Investigator(Kenkyū-buntansha) |
YANAGISAWA Akira Nagoya University, Faculty of Engineering, Assistant Professor, 工学部, 助手 (60183117)
MARUOKA Keiji Nagoya University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (20135304)
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| Project Period (FY) |
1991 – 1992
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| Project Status |
Completed (Fiscal Year 1992)
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| Budget Amount *help |
¥6,900,000 (Direct Cost: ¥6,900,000)
Fiscal Year 1992: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1991: ¥6,200,000 (Direct Cost: ¥6,200,000)
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| Keywords | Lewis Acidic Receptor / Organoaluminums / Molecular Recognition / Complexation Chromatography / Diels-Alder Reaction / Chiral Organoaluminums / Binaphthols / Asymmetric Claisen Rearrangement / 不斉ディールズ・アルダー反応 / ルイス酸型レセプタ- / 複合体形成クロマトグラフィ- / ディ-ルズ・アルダ-反応 |
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| Research Abstract |
Exceptionally bulky, oxygenophilic methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) can be utilized as a Lewis acidic receptor for complexation with a series of carbonyl compounds, ether, and epoxides. By using low-temperature ^<13>C NMR spectroscopy, MAD was found to coordinate strongly to oxygen-containing substrates in the order of amides, aldehydes, ketones or esters, epoxides, and ethers. Even structurally very similar carbonyl compounds can be easily separated by MAD. This observation enabled the highly regio- and stereocontrolled Diels-Alder reaction of unsymmetrical fumarates based on the discrimination of two different fumarate carbonyls with MAD. The high recognition ability of MAD is successfully applied to the clean separation of structurally very similar ethers by complexation chromatography using MAD-type, polymeric organoaluminum reagents. This polymeric organoaluminum column is also employable as solid-state reactor for catalytic rearrangement of epoxides to carbonyl compounds. Based on the molecular recognition chemistry with MAD, a new type of chiral organoaluminum reagents have been developed which are prepared from trimethylaluminum and optically active 3,3'-bis(triarylsilyl)binaphthols. These chiral organoaluminum reagents are highly useful for asymmetric Claisen rearrangement of allylic vinyl ethers and asymmetric Diels-Alder reaction of dienes and unsaturated esters.
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