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1996 Fiscal Year Final Research Report Summary

Development of a new molecular recognition chemistry using Lewis acidic receptors

Research Project

Project/Area Number 06403024
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionNagoya University

Principal Investigator

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

Co-Investigator(Kenkyū-buntansha) SAITO Susumu  Nagoya University, Graduate School of Engineering, Research Associate, 工学部, 助手 (90273268)
ISHIHARA Kazuaki  Nagoya University, Graduate School of Engineering, Assistant Professor, 工学部, 助手 (40221759)
YANAGISAWA Akira  Nagoya University, Graduate School of Engineering, Associate Professor, 工学部, 助教授 (60183117)
Project Period (FY) 1994 – 1996
KeywordsLewis acidic receptor / Aluminum reagent / Designer Lewis acid / Lewis base / Selective organic synthesis / Molecular recognition chemistry / Lewis acid-base complex
Research Abstract

The fascination of molecular recognition chemistry is extending continuously, especially as host-guest systems which mimic biologically occurring compounds exhibiting catalytic activities like enzymes. The discovery of crown ethers and cryptands and their inclusion systems by Prof. Lehn and Cram led them to be the winners of the Nobel Prize, and most of these systems are constituted by hydrogen-bonding networks between host and guest molecules. Comparing with these weak interactions, relatively strong coordination bonding between Lewis acidic receptors and Lewis bases has received less attention for molecular recognition, and has never been used for selective organic synthesis.
In this context, we have developed several bulky organoaluminum reagents which have sterically hindered phenoxide ligands. These bulky aluminum reagents are monomeric in solution, thereby possess strong Lewis acidity to bind a variety of heteroatom-containing substrates such as carbonyl, carboxyl and amide compounds. The complexation is sometimes stereo-, regio-, and chemoselective, leading to selective organic reactions which could not be realized with other ordinary Lewis acicls such as AlCl_3, SnCl_4, BF_3, and TiCl_4. In particular, aluminum tris(2,6-diphenylphenoxide(ATPH) was explored recently for obtaining unprecedented reactivity and selectivity n several reactions. 1. Conjugate addition of carbanions to alpha, beta-unsaturated aldehydes 2. Exo-selective Diels-Alder reactions 3. Stereo-and asymmetric Claisen rearrangement 4.1,6-Addition to aromatic carbonyl substrates.

  • Research Products

    (15 results)

All Other

All Publications (15 results)

  • [Publications] 丸岡啓二: "Crganoaluninvm-Premoted Hemologation at Ketenes with Diazealkanes" J. Crg. Chem.59(17). 4725-4726 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 丸岡啓二: "Virtualy Complete Blocking at αβ-Unsaturated Aldehydes Carbonyls by Complexation with Aluminum Tris (216-diphenylphenoxide)" J. Am. Chem. Soc.116(9). 4131-4132 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 丸岡啓二: "Exo-Selective Diels-Alder Reaction Based on a Molecular Recognition Approach" J. Am. Chem. Soc.116(26). 12115-12116 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 丸岡啓二: "Molecular Design of a Chiral Lewis Acid for the Asymmetric Claisen Rearrangement" J. Am. Chem. Soc.117(3). 1165-1166 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 丸岡啓二: "Unprecedented Nucleophilic Addition of Organolithiums to Aroinatic Aldehydes and Ketones by Complexation with Aluminum Tris (216 diphenylphenoxide)" J. Am. Chem. Soc.117(35). 9091-9092 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 斎藤進: "Efficient Conjugate Reduction of αβ-Unsaturated Corhonyl Compounds by Complexation with Aluminum Tris (216-diphenylphenoxide) (ATPH)" J. Org. Chem.61(9). 2928-2929 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Maruoka, A.B.Concepcion, H.Yamamoto: "Organoaluminum-Promoted Homologation of Ketones with Diazoalkanes." J.Org.Chem. 59(17). 4725-4726 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Maruoka, H.Imoto, S.Saito, H.Yamamoto: "Virtually Complete Blocking of alpha, beta-Unsaturated Aldehydes Carbonyls by complexation with Aluminum Tris(2,6-diphenylphenoxide)." J.Am.Chem.Soc.116(9). 4131-4132 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Maruoka, M.Akakura, S.Saito, T.Ooi, H.Yamamoto, Asymmetric Diels-Alder Reaction of Unsymmetrical Maleates.: "A chemical Access to Chiral, Unsymmetrical Cis-cyclohexane-1,2-dicarboxylates" J.Am.Chem.Soc.116(4). 6153-6158 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Maruoka, S.Saito, H.Yamamoto: "Aluminum Tris(2,6-diphenylphenoxide)(ATPH)as an Extemely Selective Activator of Less Hindered Aldehyde Carbonyls" Synlett. (6). 439-440 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Maruoka, H.Imoto, H.Yamamoto: "Exo-Selective Diels-Alder Reaction Based on a Molecular Recognition Approach." J.Am.Chem.Soc.116(26). 12115-12116 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Maruoka, S.Saito, H.Yamamoto: "Molecular Design of a Chiral Lewis Acid for the Asymmetric Claisen Rearrangement" J.Am.Chem.Soc.117(3). 1165-1166 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Maruoka, M.Ito, H.Yamamoto: "Unprecedented Nucleophilic Addition of Organolithiums to Aromatic Aldehydes and Ketones by Complexation with Aluminum Tris(2,6-diphenylphenoxide)" J.Am.Chem.Soc.117(35). 9091-9092 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Saito, H.Yamamoto: "Efficient Conjugate Reduction of alpha, beta-Unsaturated Carbonyl Compounds by Complexation with Aluminum Tris(2,6-diphenylphenoxide)(ATPH)." J.Org.Chem.61(9). 2928-2929 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Saito, K.Shimada, H.Yamamoto: "Aluminum Tris(4-bromo-2,6-diphenylphenoxide)(ATPH-Br) : Effective Catalyst for Claisen Rearrangement." Synlett. (8). 720-722 (1996)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1999-03-09  

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