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Development of Efficient Methods for the Synthesis of Medium- and Large-Sized Carbocycles with the Aid of Samarium

Research Project

Project/Area Number 02453026
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionOkazaki National Research Institutes

Principal Investigator

INANAGA Junji  O. N. R. I., IMS., Associate Professor, 分子科学研究所, 助教授 (50091244)

Co-Investigator(Kenkyū-buntansha) HANAMOTO Takeshi  O. N. R. I., IMS, Research Associate, 分子科学研究所, 助手 (20228513)
Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 1991: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1990: ¥4,300,000 (Direct Cost: ¥4,300,000)
KeywordsSamarium (II) Iodide / Medium-Sized Carbocycle / Large-Sized Carbocycle / Cyclization / Reductive Dimerization / Intramolecular Pinacol Coupling / Lanthanide Triflate / Intramolecular Reformatsky Reaction / 中員炭素環化合物 / ピナコ-ルカップリング / ヨウ化サマリウム
Research Abstract

Medium- as well as large-sized carbocyclic compounds whose ring skekitorls are composed entirely of sp^3 carbons have been prepared in high yields under mild conditions by utilizing Sml_2-promoted intramolecular Reformatsky reaction. The reaction seems to proceed through samarium enorate intermediate as the result of successive two-ekx-tron reduction of a-bromo esters. The distinct property of samarium such as large ionic radius, flexible coordination, and high oxophilicity should play an important role for the cyclizadion : The samarium-linked large-sized chelate, from which the carbon-carbon bond formation would take place like a ring contraction, and the six-membered chelate after cyclization might be involved in the process.
Conjugated esters were instantaneously hydrodimerized at room temperature by use of the reduction system, Sml_2-THF-HMPA, in the presence of proton sources, and perfect stereoselection was realized in the reaction of N, N-dibenzyl crotonamide. However, the method could riot be successfully applied to macrocyclization. In connection with the present study, a very efficient method for the selective reduction of alpha, beta-unsaturated esters and amkles via Sml_2-promoted electron transfer process was also developed.
Pinacol coupling reaction with lanthanide triflate-samarium (II) iodide system afforded medium-sized carbocycle in moderate yield in the preliminary experiment. This approach seems to be promising and is being further studied in this laboratory.
All other efforts to develop useful cyclization methods to botain medium-sized carbocycles ended in failure : The attempted methods are (i) intramolecular Barbier-type reaction of w-oxo allylic halides, (ii) acyloin condensation, and (iii) ketone-alkene or ketone-alkyne reductive coupling reaction. But, the last method was found to be useful as carboncarbon bond-forming reaction via radical process.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] T.Hanamoto,J.Inanaga: "Sml_2-Promoted Ketyl Radical Addition to O-Benzyl Formaldoxime.A New Aminomethylation" Tetrahedron Letters. 32. 3555-3556 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J.Inanaga,J.Katsuki,O.Ujikawa,M.Yamaguchi: "Carbon-Carbon Bond Formation by Intermolecular Radical Reaction.Sml_2-Promoted Carbonyl-Alkyne Reductive Coupling" Tetrahedron Letters. 32. 4921-4924 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J.Inanaga,Y.Yokoyama,Y.Handa,M.Yamaguchi: "Preparation of Medium-and Large-Sized Carbocycles by Means of Sml_2-Promoted Intramolecular Reformatsky Reaction" Tetrahedron Letters. 32. 6371-6374 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J.Inanaga,Y.Handa,T.Tabuchi,K.Otsubo,M.Yamaguchi,T.Hanamoto: "A Facile Reductive Dimerization of Conjugated Acid Derivatives with Samarium Diiodide" Tetrahedron Letters. 32. 6557-6558 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J.Inanaga,S.Sakai,Y.Handa,M.Yamaguchi,Y.Yokoyama: "Selective Conjugate Reduction of α,β-Unsaturated Esters and Amides via Sml_2-Promoted Electron Transfer Process" Chemistry Letters. 2117-2118 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J.Inanaga,Y.Yokoyama,T.Hanamoto: "Pinacol Coupling with Lanthanide Triflate-Samarium(II) lodide System"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J.Inanaga: "Trends in Organic Chemistry,Vol.1" Council of Scientific Research Integration, 8 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Hanamoto, J. Inanaga: "Sml_2-Promoted Ketyl Radical Addition to OMICRON-Benzyl Formaldoxime. A New Aminomethylation" Tetrahedron Lett.32. 3555-56 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J. Inanaga, J. Katsuki, O. Ujikawa, M. Yamaguchi: "Carbon-Carbon Bond Formation by intermolecular Radical Reaction. Sml_2-Promoted Carbonyl-Alkyne Reductive Coupling" Tetrahedron Lett.32. 4921-24 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J. Inanaga, Y. Yokoyama, Y. Handa, M. Yamaguchi: "Preparation of Modium- and Large-Sized Carbocycles by Means of Sml_2-Promoted Intramolecular Reformatsky Reaction" Tetrahedron Lett.32. 6371-74 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J. Inanaga, Y. Handa, T. Tabuchi, K. Otsubo, M. Yamaguchi, T. Hanamoto: "A Facile Reductive Dimerization of Conjugated Acid Derivatives with Samarium Diiodide" Tetrahedron Lett.32. 6557-58 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J. Inanaga, S. Sakai, Y. Handa, M. Yamaguchi, Y. Yokoyama: "Selective Conjugate Reduction of alpha, beta-Unsaturated Esters and Amides via Sml_2-Promoted Electron Transfer Process" Chemistry Lett.2117-18 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J. Inanaga, Y. Yokoyama, T. Hanamoto: "Pinacol Coupling with Lanthanide Triflate-Samarium (II) Iodide System"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J. Inanaga: "Carbon-Carbon Bond Formation via Sml2-Promoted Electron Transfer Process" Trends in Organic Chemistry. 1. 23-30 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] J.Inanaga,Y.Yokoyama,T.Hanamoto: "Pinacol Coupling with Lanthanide Triflate-Samarium(II)lodide System"

    • Related Report
      1991 Annual Research Report
  • [Publications] Junji Inanaga: "Formation of Mediumーand LargeーSized Carbocyclic Compounds by Means of SmI_2ーPromoted Intramolecular Reformatsky Reaction" Tetrahedron Letters.

    • Related Report
      1990 Annual Research Report
  • [Publications] Junji Inanaga: "A Facile Reductive Dimerization of Conjugated Acid Derivatives with Samarium Diiodide" Tetrahedron Letters.

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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