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Development of New Molecular Recognition Chemistry using Organoaluminums

Research Project

Project/Area Number 03453100
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionNagoya University

Principal Investigator

YAMAMOTO Hisashi  Nagoya University, Faculty of Engineering, Professor, 工学部, 教授 (10135311)

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)
Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
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)
KeywordsLewis 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
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.

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] 長原 滋,山本 尚,丸岡 啓二: "ルイス酸型レセプターによる分子認識" 化学. 46. 204-205 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiji Maroka,Susumu Saito,Hisashi Yamamoto: "Discrimination of Two Different Ester Carbonyls with MAD:Application to the Regio-and Stereocontrolled Diels-Alder Reaction of Unsymmetrical Fumarates" Jounal of the American Chemical Society. 114. 1089-1090 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Sigeru Nagahara,Keiji Maruoka,Hisashi Yamamoto: "A Highly Efficient Separation of Structurally Similar Epoxy Silyl Ethers by Complexation Chromatography on polymeric Organoaluminum Reagents" Tetrahedron Letters. 33. 527-530 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Shigeru Nagahara,Keiji Maruoka,Hisashi Yamamoto: "A Facile Workup-Free Catalytic Rearrangement of Epoxides on Immobilized Organoaluminum Columns" Chemistry Letters. 1193-1196 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiji Maruoka,Arnel B.Concepcion,Hisashi Yamamoto: "Asymmetric Diels-Alder Reaction of Cyclopentadiene and Methyl Acrylate Catalyzed by Chiral Organoaluminum Reagents" Bulletin of the Chemical Society of Japan. 65. 3501-3503 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Shigeru Nagahara, Hisashi Yamamoto, and Hisashi Yamamoto: "Molecular Recognition using Lewis Acidic Receptors" Kagaku. 46. 204-205 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiji Maruoka, Susumu Saito, and Hisashi Yamamoto: "Discrimination of Two Different Ester Carbonyls with MAD: Application to the Regio- and Stereocontrolled Diels-Alder Reaction of Unsymmetrical Fumarates" J. Am. Chem. Soc.114. 1089-1090 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Shigeru Nagahara, Keiji Maruoka, and Hisashi Yamamoto: "A Highly Efficient Separation of Structurally Similar Epoxy Silyl Ethers by Complexation Chromatography on Polymeric Organoaluminum Reagents" Tetrahedron Lett.33. 527-530 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Shigeru Nagahara, Keiji Maruoka, and Hisashi Yamamoto: "A Facile Workup-Free Catalytic Rearrangement of Epoxides on Immobilized Organoaluminum Columns" Chem. Lett.1193-1196 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiji Maruoka, Arnel B. Concepcion, and Hisashi Yamamoto: "Asymmetric Diels-Alder Reaction of Cyclopentadiene and Methyl Acrylate Catalyzed by Chiral Organoaluminum Reagents" Bull. Chem. Soc. Jpn.65. 3501-3503 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiji Maruoka Susumu Saito Hisashi Yamamoto: "Discrimination of Two Different Ester Carbonyls with MAD:Application to the Regio-and Stereocontrolled Diels-Alder Reaction of Unsymmetrical Fumarates" Journal of the American Chemical Society. 114. 1089-1090 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Sigeru Nagahara Keiji Maruoka Hisashi Yamamoto: "A Highly Efficient Separation of Structurally Similar Epoxy Silyl Ethers by Complexation Chromatography on Polymeric Organoaluminum Reagents" Tetrahedron Letters. 33. 527-530 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Shigeru Nagahara Keiji Maruoka Hisashi Yamamoto: "A Facile Workup-Free Catalytic Rearrangement of Epoxides on Immobilized Organoaluminum Columns" Chemistry Letters. 1193-1196 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Keiji Maruoka Arnel B.Concepcion Hisashi Yamamoto: "Asymmetric Diels-Alder Reaction of Cyclopentadiene and Methyl Acrylate Catalyzed by Chiral Organoaluminum Reagents" Bulletin of the Chemical Society of Japan. 65. 3501-3503 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 長原 滋,山本 尚,丸岡 啓二: "ルイス酸型レセプタ-による分子認識" 化学. 46. 204-205 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Keiji Maruoka,Junko Sato,Hisashi Yamamoto: "Practical Asymmetric Synthesis of Both Erythro and threo Aldols:Unusual Effect of Silyl Groups" Journal of the American Chemical Society. 113. 5449-5450 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Keiji Maruoka,Takashi Ooi,Shigeru Nagahara,Sato Hisashi Yamamoto: "OrganoaluminumーCatalyzed Rearrangement of Epoxides.A Facile Route to the Synthesis of Optically Active betaーSiloxy Aldehydes" Tetrahedron. 47. 6983-6998 (1991)

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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