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New Successive Reactions Utilizing Functional Carbanions

Research Project

Project/Area Number 13672217
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionThe University of Tokushima

Principal Investigator

SHINDO Mitsuru  The University of Tokushima, Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (40226345)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 2002: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2001: ¥2,500,000 (Direct Cost: ¥2,500,000)
Keywordsvnolate / cycloaddition / alkene / stereoselective synthesis / tandem reaction / β-lactone enolate / Michael reaction / polvsubstituted carbocycle / アルゲン / イノラートアニオン / オレフィン化反応 / カスケード反応 / セスキテルペン / 立体電子効果 / cucumin E / ベータラクトン
Research Abstract

Ynolates are ketene anion equivalens, so that ynolates are converied into reactive species after the first reaction. Using this property, novel successive reactions as well as new synthetic method of ynolates have been developed
1. Practical synthetic method of ynolates: Naphithalene catalyzed reductive lithation of dibromo esters leading ynolates was developed.
2. Highly Z-selective synthesis of alkenes via tandem [2+2] cycloaddition - ring-opening reaction: Ynolates reacted with acylsilanes to afford polysubstituted vinyl silanes with perfect Z-selectivity. These vinyl silanes produced can be converted into tetrasubstituted alkenes. Ynolates reacted with α-oxyketones to give tetrasubsituted alkenes with high Z-selectivity. These prodeucts were easily converted into butenolides by treatment of acids. This 2-step conversion prosess can be carried out in one-pot.
3. Efficient syntheses of carbocycles via tandem [2+2] cycloaddition - Michael reaction: β-Lactone enolates prepared by reaction of ynolates with ketones have high nucleophiliciy. The reaction of ynolates with ketones having an unsaturated eater unit in a proper positionprovided bicyclic β-lactones via tandem [2+2] cycloaddition - Michael addition. The products were easily converted to polysubstituted cycloalkenes in good yield. By this tandem reaction, five-, six- and seven-membered carbocycles can be constructed. Since the products of the tandem reaction are ester enolates, they have uncleophilicity. Taking advantage of this properties, cascade reactions can be carried out to give complex molecules.
4. Total synthesis of cucumin E, novel type of triquinane sesquiterpenoid, was achieved using the tandem reaction.

Report

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

    (37 results)

All Other

All Publications (37 results)

  • [Publications] M.Shindo: "The first tandem [2+2] cycloaddition -Michael reaction using ynolates : facile construction of substituted carbocycles"Organic Letters. 3. 2029-2031 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "Practical synthesis of ynolate anions : naphthalene-catalyzed reductive lithiation of α,α-dibromoesters"Tetrahedron Letters. 42. 8357-8360 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "A novel tandem [2+2] cycloaddition -Dieckmann condensation with ynolate anions. Efficient synthesis of substituted cycloalkenones and naphthalenes via formal [n+1] cycloaddition"The Journal of Organic Chemistry. 66. 7818-7824 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] W.Yokota: "Synthetic studies on Halichlorine and pinnaic acid : palladium mediated construction of the bicyclic spiro core"Heterocycles. 54. 871-885 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Sato: "Total synthesis of (-)-Heliannuol E"The Journal of Organic Chemistry. 66. 309-314 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Yuki: "Enantioselective total synthesis of (-)-equisetin using a Me_3Al-mediated intramolecular Diels-Alder reaction"Tetrahedron Letters. 42. 2517-2519 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "The First General Method for Z-Selective Olefination of Silyl Ketones via Ynolate Anions Providing Multisubstituted Alkenes"Journal of the American Chemical Society. 124. 6840-6841 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "An ynolate-initiated tandem process giving cyclopentenones : total synthesis of cucumin E"Tetrahedron Letters. 43. 5039-5041 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "Anionic Inverse Electron-Demand 1,3-Dipolar Cycloaddition of Nitrones with Ynolates. Facile Stereoselective Synthesis of 5-Isoxazolidinones Leading to β-Amino Acids"Organic Letters. 4. 3119-3121 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Fukuda: "Diastereoselective Ring Closing Metathesis for the Construction of a Quaternary Carbon Stereogenic Center"Tetrahedron Letters. 43. 2047-2049 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Itoh: "Apoptosis-Inducing Activity of Synthetic Intermediates of Halichlorine"Bioorganic Medicinal Chemistry Letters. 12. 2069-2072 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Kisyuku: "Enantioselective total synthesis of (-)-heliannuol A"Chemical Communications. 350-351 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "The first tandem [2+2] cycloaddition - Michael reaction using ynolates: facile construction of substituted carbocycles"Organic Letters. 3. 2029-2031 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "Practical synthesis of ynolate anions: naphthalene-catalyzed reductive lithiation of α, α-dibromoesters"Tetrahedron Letters. 42. 8357-8360 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "A novel tandem [2+2] caycloaddition - Dieckmam condensation with ynolate anions. Efficient synthesis of substrituted cycloalkenones and naphthalenes via formal [n+1] cycloaddition"The Journal of Organic Chemistry. 66. 7817-7824 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] W.Yokota: "Synthetic studies on Halichlorine and pinnaic acid: palladium mediated construction of the bicyclic spiro core"Heterocycles. 54. 871-885 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Sato: "Total synthesis of (-) -Heliannuol E"The Journal of Organic Chemistry. 66. 309-314 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Yuki: "Enantioselective total systhesis of (-)-equisetin using a Me_3Al-mediated intramolecular Diels-Alder reaction"Tetrahedron Letters. 42. 2517-2519 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "The First General Method for Z-Selective Olefination of Silyl Ketones via Ynolate Anios Providing Multisubstituted Alkenes"Journal of the American Chemical Society. 124. 6840-6841 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "An ynolate-initlated tandem process giving cyclopentenones: total synthesis of cucumin E"Tetrahedron Letters. 43. 5039-5041 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "Anionic Inverse Electron-Demand 1,3-Dipolar Cycloaddition of Nitrones with Ynolates. Facile Stereoselective Synthesis of 5-Isoxazolidinones Leading to β-Amino Acids"Tetrahedron Letters. 43. 2047-2049 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Itoh: "Apoptosis-Inducing Activity of Synthetic Intermediates of Halichlornie"Bioorganic Medicinal Chemistry Letters. 12. 2069-2072 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Kisyuku: "Enantioselective total synthesis of (-)-heliannuol A"Chemical Communications. 350-351 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "Synthesis of α,α-Dibromo Eaters as Precursors of Ynolates"Chem. Pham. Bull. in press.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Shindo: "The First General Method for Z-Selecive Olefination of Silyl Ketones via Ynolate Anions Providing Multisubstituted Alkenes"Journal of the American Chemical Society. 124. 6840-6841 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Shindo: "An ynolate-initiated tandem process giving cyclopentenones : total synthesis of cucumin E"Tetrahedron Letters. 43. 5039-5041 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Shindo: "Anionic Inverse Electron-Demand 1,3-Dipolar Cycloaddition of Nitrones with Ynolates. Facile Stereoselective Synthesis of 5-Isoxazolidinones Leading to β-Amino Acids"Organic Letters. 4. 3119-3121 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Fukuda: "Diastereoselective Ring Closing Metathesis for the Construction of a Quaternary Carbon Stereogenic Center"Tetrahedron Letters. 43. 2047-2049 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Itoh: "Apoptosis-Inducing Activity of Synthetic Intermediates of Halichlorine"Bioorganic Medicinal Chemistry Letters. 12. 2069-2072 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Kisyuku: "Enantioselective total synthesis of (-)-heliannuol A"Chemical Communications. 350-351 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.shindo: "Synthesis of α, α-Dibromo Esters as Precursors of Ynolates"Chem. Pharm. Bull. (印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Shindo, M.: "The first tandem [2+2] cycloaddition-Michael reaction using ynolates : facile construction of substituted carbocycles"Organic Letters. 3. 2029-2031 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Shindo, M.: "Practical synthesis of ynolate anions : naphthalene-catalyzed reductive lithiation os α, α-dibromoesters"Tetrahedron Letters. 42. 8357-8360 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Shindo, M.: "A novel tandem [2+2] cycloaddition-Dieckmann condensation with ynolate anions. Efficient synthesis of substituted cycloalkenones and naphthalenes via formal [n+1] cycloaddition"The Journal of Organic Chemistry. 66. 7818-7824 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yokota, W.: "Synthetic studies on Halichlorine and pinnaic acid : palladium mediated construction of the bicyclic spiro core"Heterocycles. 54. 871-885 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Sato, K.: "Total synthesis of(-)-Heliannuol E"The Journal of Organic Chemistry. 66. 309-314 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yuki, K.: "Enantioselective total synthesis of(-)-equisetin using a Me3Al-mediated intramolecular Diels-Alder reaction"Tetrahedron Letters. 42. 2517-2519 (2001)

    • Related Report
      2001 Annual Research Report

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

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