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A New Synthesis of Polyquinanes Utilizing alpha-Ketovinylphosphonates

Research Project

Project/Area Number 03650706
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKyushu Institute of Technology

Principal Investigator

MINAMI Toru  Professor, 工学部, 教授 (10029134)

Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1992: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1991: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsCyclopentanoids / Vinylphosphonates / Nazarov Cyclization / 1,3-Dipolar Addition / Terpenoids / Ene Reaction / Lewis Acids / Wittig Reaction / 縮環化合物 / ニトロン / アゾメチンイミン / 1ーケトビニルホスホナ-ト / ダブルマイケル付加 / 分子内HornerーWittig反応 / ジビニルケトン / ジキナン誘導体 / トリキナン誘導体
Research Abstract

This project is composed of three subjects as mentioned below. (1) Convenient Synthesis of Functionalized Cyclopentanoids
A new approach to cyclopentane annulated compounds was successfully achieved by using 1-(cyclopent-1-enylcarbonyl)vinylphosphonates 1, which we newly developed. Treatment of 1 with Lewis acids or polyphosphoric acid led to 2-phosphorylcyclopentenone annulated compounds in 25-71% yields. The Michael addition of (1,3-dioxolan-2-yl)ethylmagnesium bromide to 1, followed by acidic hydrolysis and the intramolecular Wittig-Horner reaction gave divinyl ketones 2 (51-70%). Nazarov cyclization of 2 produced cyclopentane annulated compounds 3 in good yields. (2) Arylation of Phosphonate Carbanions and Synthetic Application of alpha-Arylmethylphosphonates
Copper(I)-catalyzed reaction of phosphonate carbanions with aryliodides in DMF gave alpha-arylated phosphonates in good yields. Functionalized dihydroisoquinoline N-oxides and N-phenyl(or alkyl) imines were synthesized from alpha-(o-formylphenyl)methyl-phosphonates prepared, paraformaldehyde, and oxime or hydrazines. 1,3-Dipolar cycloaddition of the 1,3-dipoles to dipolarophiles gave the cycloadducts. (3) Synthesis of Cyclic Terpenoids via Intramolecular Ene Reaction of Vinylphosphonates
Lewis acid promoted intramolecular ene reaction of the vinylphosphonates, prepared from citronellal or 2,6-dimethyl-5-heptenal and triethyl phosphonoacetate, gave stereoselectively cyclic terpenoids bearing the phosphono group in good yields. The wittig reaction of the terpenoids with paraformaldehyde, followed by intramolecular ene reaction provided the bicyclic terpenoids in good to moderate yields.

Report

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

    (13 results)

All Other

All Publications (13 results)

  • [Publications] T.Minami: "A New Approach to Cyclopentane Annulated Compounds via 1-(Cyclopent-1-enylcarbonyl)vinylphosponates" J.Cehm.Soc.,Chem.Commun.1992. 190-191 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Minami: "Vinylphosphonates in Organic Synthesis" Synthesis. 1992. 333-349 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] J.Ichikawa: "A Novel Synthesis of 2,2-Difluorovinyl-and 2-Fluorovinylphosphorus Compounds from 2,2,2-Trifluoroethyl p-Toluenesulfonate" Synlett.1992. 833-834 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Minami: "Synthesis of Annulated γ-Lactams via Intramolecular 1,3-Dipolar Cycloadditions of Functionalized N-Allyl α-Diazo Amides" Bull.Chem.Soc.Jpn.66. (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Minami et al.: "A New Approach to Cyclopentane Annulated Compounds via 1-(Cyclopent-1-enylcarbonyl)-vinylphosphonates" J. Chem. Soc., Chem. Commun.1992. 190-191 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Minami et al.: "Vinylphosphonates in Organic Synthesis" Synthesis. 1992. 333-349 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] J.Ichikawa et al.: "A Novel Synthesis of 2,2-Difluorovinyl-and 2-Fluorovinylphosphorus Compounds from 2,2,2-Trifluoroethyl rho-Toluenesulfonate" Synlett.1992. 833-834 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Minami et al.: "Synthesis of Annulated gamma-Lactams via Intramolecular 1,3-Dipolar Cycloadditions of Functionalized N-Allyl alpha-Diazo Amides" Bull. Chem. Soc. Jpn.66. (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Minami: "A New Approach to Cyclopentane Annulated Compounds via 1‐(Cyclopent‐1‐enylcarbonyl)vinylphosphonates" J.Chem.Soc.,Chem.Commun.1992. 190-191 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Minami: "Vinylphosphonates in Organic Synthesis" Synthesis. 1992. 333-349 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] J.Ichikawa: "A Novel Synthesis of 2,2‐Difluorovinyl‐and 2‐Fluorovinylphosphorus Compounds from 2,2,2‐Trifluoroethyl р‐Toluenesulfonate" Synlett.1992. 833-834 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Minami: "Synthesis of Annulated γ‐Lactams via Intramolecular 1,3‐Dipolar Cycloadditions of Functionalized N‐Allyl α‐Diazo Amides" Bull.Chem.Soc.Jpn.66. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Minami,M.Nakayama,K.Fujimoto,S.Matsuo: "A New Approach to Cyclopentane Annulated Compounds via 1ー(Cyclopentー1ーenylcarbonyl)vinylphosphonates" J.Chem.Soc.,Chem.Commun.190-191 (1992)

    • Related Report
      1991 Annual Research Report

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

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