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Development of Cationic Transition Metal Complex-Catalyzed Asymmetric [2+2] Cycloaddition Reaction

Research Project

Project/Area Number 13650908
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

HATTORI Tetsutaro  Toboku University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (70241536)

Co-Investigator(Kenkyū-buntansha) MIYANO Sataro  Tohoku University, Graduate School of Engineering Professor, 大学院・工学研究科, 教授 (60005501)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2001: ¥2,000,000 (Direct Cost: ¥2,000,000)
Keywords[2+2] cycloaddition reaction / Lewis acid catalysts / cationic palladium complexes / oxetan-2-ones / 3,6-dihydro-2H-pyran-2-ones / asymmetric synthesis / CO_2 fixation / tandem [2+2] cycloaddition-allylic rearrangement / キラルカウンターアニオン / 3,6-ジヒドロー2H-ピラン-2-オン / 4-ビニルオキセタン-2-オン
Research Abstract

1.[2+2] Cycloaddition reaction of carbonyl compounds with ketene The [2+2] cycloaddition reaction was examined by using some cationic group 8-10 transition metal complexes as the catalysts, among which palladiun and platinum complexes showed good perfonnance. It was found that the catalytic activity was greatly affected not only by the metal center and the ligand but also by the counter anion. Attempts on asymmetric induction by using chiral ligands failed but chiral counterions, tetraalkoxy borates derived from substituted BINOLs, were found to serve as a chirality-recognizing element in the asymmetric reaction.
2.Tandem [242] cycloaddition-allylic rearrangement or α,β-unsaturatead carbonyl compounds with ketene In the reaction of α,β-unsaturated carbonyl compounds, 4-vinyloxetan-2-ones generated by the cycloaddition oflen rearrange under the conditions to give 3,6-dihydro-2H-pyran-2-ones. Thus, the reaction of a series of α,β-unsaturated aldehydes and ketones with ketene was examined to deduce the origin of the rearrangement. It was found that the reaction occurs if 4-vinyloxetan-2-ones bearing an alkyl substituent at the 4-position or at the 2-position of the vinyl moiety are generated in the cycloaddition. Based on the observations, a reacfion mechanism was proposed, which includes a zwitterion generated by heterolytic cleavage of the C(4)-0 bond of the 4-vinyloxetan-2-one as an intermediate. Asymmetric induction with up to 57% de has been achieved by using α,β-unsaturated aldehydes bearing an asymmetric carbon center at the β-position.
3.Activation of CO_2 by Lewis acids and its chemical fixation to carbon-carbon double bonds As an extension of this research project, a possibility was examined to activate C0_2 by aluminum-based Lewis acids and fix it electrophilically to aromatic compounds and organosilanes, which might lead to an alternative method to prepare oxetan-2-ones from olefins and CO_2 in the future.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (32 results)

All Other

All Publications (32 results)

  • [Publications] T.Hattori: "Synthesis of3,6-dihydro-2H-pyran-2-ones via cationic palladium(II) complex-catalyzed tandem[2+2] cycloaddition-allylic rearrangement of ketene with α,β-unsaturated aldehydes and ketones"Tetrahedron. 58. 5215-5223 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Suzuki: "Lewis Acid-Mediated Carboxylation of Fused Aromatic Compounds with Carbon Dioxide"Chem.Lett.. 102-103 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori: "Lewis Acid-Mediated Carboxylation of Aryl-and Allylsilanes with Carbon Dioxide"Chem.Lett.. 32. 454-455 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori: "Nucleophilic aromatic substitution on 1-alkoxy-2-nitronaphthalene by 1-naphthyl Grignard reagents for the synthesis of 2-nitro-1, 1'-binaphthyls"Tetrahedron. 58. 233-238 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Morohashi: "Dinuclear titanium(IV) complex ofp-tert-butylthiacalix[4]arene as a novel bidentate Lewis acid catalyst"Tetrahedron Lett.. 43. 7769-7772 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Morohashi: "Synthesis of All Stereoisomers of Sulfinylcalix[4]arenes"J.Org.Chem.. 68. 2324-2333 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori: "Use of a racemic derivatizing agent for measurement of enantiomeric excess by circular dichroism spectroscopy"Tetrahedron Lett.. 42. 8015-8018 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori: "Highly stereospecific conversion of C-centrochirality of a 3,4-dihydro-2H-1, 1'-binaphthalen-1-ol into axial chirality of a 3,4-dihydro-1,1'-binaphthalene"Tetrahedron Lett.. 42. 8035-8038 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] E.Koshiishi: "7-Mesityl-2,2-dimethylindan-1-ol : a novel alcohol which serves as both a chiral auxiliary and a protective group for carboxy functions"J.Chem.Soc., Perkin Trans.1. 377-383 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori: "First determination of the absolute stereochemistry of a naturally occurring 1,1'-biphenanthrene, (-)-blestriarene C, and its unexpected photoracemization"Chem.Commun.. 2234-2235 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] F.Narumi: "Synthesis and Optical Resolution of an anti-O, O'-Dialkylated Calix[4]arene"Chem.Lett. 32. 320-321 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori: "Synthesis, Resolution, and Absolute Stereochemistry of (-)-Blestriarene C"J.Org.Chem.. 68. 2099-2108 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori, Y.Suzuki, Y.Ito, D.Hotta, and S.Miyano: ""Synthesis of 3,6-dihydro-2H-pyran-2-ones via cationic palladium(II) complex-catalyzed tandem [2+2] cycloaddition-allylic rearrangement of ketene with α,β-unsaturated aldehydes and ketones.""Tetrahedron. 58. 5215-5223 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Suzuki, T.Hattori, T.Okuzawa, and S.Miyano: ""Lewis Acid-Mediated Carboxylation of Fused Aromatic Compouds with Carbon Dioxide.""Chem.Lett.. 102-103 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori, Y.Suzuki, and S.Miyano: ""Lewis Acid-Mediated Carboxylation of Aryl- and Allylsilanes with Carbon Dioxide.""Chem.Lett.. 32. 454-455 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori, A.Takeda, O.Yamabe, and S.Miyano: ""Nucleophilic aromatic substitution on 1-alkoxy-2-nitronaphthalene by 1-naphthyl Grignard reagents for the synthesis of 2-nitro-1, 1'-binaphthyls.""Tetrahedron. 58. 233-238 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Morohashi, T.Hattori, K.Yokomakura, C.Kabuto, and S.Miyano: ""Dinuclear titanium(IV) complex of p-tert-butylthiacalix[4]arene as a novel bidentate Lewis acid catalyst.""Tetrahedron Lett.. 43. 7769-7772 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Morohashi, H.Katagiri, N.Iki, Y.Yamane, C.Kabuto, T.Hattori, and S.Miyano: ""Synthesis of All Stareoisomers of Sulfinylcalix[4]arenas.""J.Org.Chem.. 68. 2324-2333 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori, Y.Miinato, S.Yao, M.G.Finn, and S.Miyano: ""Use of a racemic derivatizing agent for measurement of enantiomeric excess by circular dichroism spectroscopy.""Tedrahedron Lett.. 42. 8015-8018 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori, M.Date, K.Sakurai, N.Morohashi, H.Kosugi, and S.Miyano: ""Highly stereospecific conversion of C-centrochirality of a 3,4-dihydro-2H-1, 1'-binaphthalen-1-o1-into axial chiralty of a 3,4-dihydro-1, 1'-binaphthalene.""Tedrahedron Lett.. 42. 8035-8038 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] E.Koshiishi, T.Hattori, N.Ichihara, and S.Miyano: ""7-Mesityl-2, 2-dimethylindan-I-o1: a novel alcohol which serves as both a chiral auxiliary and a protective group for carboxy functions.""J.Chem.Soc., Perkin Trans.. 1. 377-383 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori, Y.Shimazumi, O.Yamada, E.Koshiishi, and S.Miyano: "First determination of the absolute stereochemistry of a naturally occurring 1,1'-biphenanthrene, (-)-blestriarene C, and its unexpected photoracemization.""Chem.Commun.. 2234-2235 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] F.Narumi, W.Yamabuki, T.Hattori, H.Kameyama, and S.Miyano: ""Synthesis and Optical Resolution of an anti-O,O'-Dialkylated Calix[4]arene.""Chem.Lett.. 32. 320-321 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori, Y.Shimazumi, H.Goto, O.Yamabe, N.Morohashi, lW.Kawai, and S.Miyano: ""Synthesis, Resolution, and Absolute Stereochernistry of (-)-BlestriareneC.""J.Org.Chem.. 68. 2099-2108 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Hattori: "Synthesis of 3,6-dihydro-2H-pyran-2-ones via cationic palladium(II) complex-catalyzed tandem [2+2] cycloaddition-allylic rearrangement of ketene with α,β-unsaturated aldehydes and ketones"Tetrahedron. 58. 5215-5223 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Hattori: "First determination of the absolute stereochemistry of a naturally occurring 1,1'-biphenanthrene, (-)-blestriarene C, and its unexpected photoracemization"Chem. Commun.. 2234-2235 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] N.Morohashi: "Dinuclear titanium(IV) complex of p-tert-butylthiacalix[4]arene as a novel bidentate Lewis acid catalyst"Tetrahedron Lett.. 43. 7769-7772 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Hattori: "Use of a Racemic Derivatizing Agent for Measurement of Enantiomeric Excess by Circular Dichroism Spectroscopy"Tetrahedron Lett.. 42. 8015-8018 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Hattori: "Highly Stereospecific Conversion of C-Centrochirality of a 3,4-Dihydro-2H-1, 1'-binaphthalen-1-ol into Axial Chirality of a 3,4-Dihydro-1, 1'-binaphthalene"Tetrahedron Lett.. 42. 8035-8038 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Hattori: "Nucleophilic Aromatic Substitution on 1-Alkoxy-2-nitronaphthalene by 1-Naphthyl Grignard Reagents for the Synthesis of 2-Nitro-1, 1'-binaphthyls"Tetrahedron. 58. 233-238 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Suzuki: "Lewis Acid-Mediated Carboxylation of Fused Aromatic Compounds with Carbon Dioxide"Chem. Lett.. 102-103 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] E.Koshiishi: "7-Mesityl-2, 2-dimethylindan-1-ol : A Novel Alcohol which Serves as Both a Chiral Auxiliary and a Protective Group for Carboxy functions"J. Chem. Soc., Perkin Trans. 1. 377-383 (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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