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A Development of New method for the Synthesis of Chiral Cyclobutanones-A Synthetic Approach to Trichothecane Type of Macrolides

Research Project

Project/Area Number 06672086
Research Category

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

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionTOHOKU UNIVERSITY

Principal Investigator

NEMOTO Hideo  Tohoku University, Faculty of Pharmaceutical, Scieneces, Research Associate, 薬学部, 助手 (60006351)

Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1995: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1994: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsCyclopropylidene / Asymmetric Epoxidation / Asymmetric Dihydroxylation / Concerted 1,2-Rearrangenmet / Chiral Cyclobutanone / 協奏的1,2転位反応 / シクロプロピチデン / 不斉エポシキ化反応
Research Abstract

Cyclobutanones consitute the basic structure of many natural products and are important intermediates in the synthesis of a wide range of natural products and other complex organic molecules. They are most often synthesized by [2+2] cycloaddition reactions between ketenes and olefins, and much effort hes been devoted to asymmetric induction in this cycloaddition process. In contrast, the studies on the asymmetric induction in the ring expansion reaction of cyclopropane rings to form cyclobutanes have been limited. We were intrigued by the possibility that the Katsuki-Sharpless asymmetric epoxidation of the cyclopropylidene alcohol might give the very labile chiral hydroxyoxaspiropentanes as initial products and then rearrange to chiral cyclobutanones in an enantiospecific manner under the reaction conditions. We therefore examined the Katsuki-Sharpless asymmetric epoxidation of cyclopropylidene alchols, which led us to develop the concise and highly enantioselective method for the synt … More hesis of chiral cyclobutanones. In the similar manner, the chiral diols derived by the asymmetric dihydroxylation of the cyclopropylidenes were found to be rearranged in enantiospecific manner to the optically active cyclobutanones via the cyclic sulfates. Based on these findings in 1994, we have been involved in the total synthesis of trichothecane type of sesquiterpenes, because the members of this class exhibit significant biological activities such as antifungal, antibacterial, antiviral, and insecticidal properties and also some of this family inhibit the growth of tumor cells. Then, we succeeded in the development of the efficient synthesis of A-ring aromatic trichothecanes, such as (2S,5S)-(-)-2-methyl-15-nor-6,8,10,12-trichothecatetraene, (-)-debromofiliformin, (-)-filiformin, (2R,5S)-15-nor-6,8,10,12-trichothecatetraene, (2R,5R,12S)-15-nor-6,8,10-trichothecatriene-12,13-diol, (2R,5R,12S)-12,13-epoxy-15-nor-6,8,10-trichothecatriene, and (2R,5R,12S)-12,13-dimethylmethylenedioxy-15-nor-6,8,10-trichothecatriene, in 1995. Less

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] 根本秀雄: "A Remarkable Substituent Effect on the Enantioselectivity of Tandem Asymmetric Epoxidation and Enantiospecific Ring Expansion of Cyclopropylidene Alcohols : A New Enantiocontrolled Synthesis of (-)-Debromoaplysin and (-)-Aplysin." J. Org. Chem.59. 74-79 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 根本秀雄: "Tandem Ring Expansion and Insertion Reaction of Alkenic Cyclobutanols Mediated by Palladium-A Novel Aooroach to Bicyclo [4. 3. 0] nonane Systems." Tetrahedron. 50. 10391-10396 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 根本秀雄: "The First Example of Asymmetric Dihydroxylation of Cyclopropylidene Derivatives-An Enantioenriched Formal Total Synthsis of (-)-Filiformin." Tetrahedron Lett.36. 1055-1058 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 根本秀雄: "A Highly Enantiocontrolled Strategy for the Synthesis of Benzylic Quaternary Carbon Centers. A Formal Total Synthesis of (-)-Mesembrine" J. Org. Chem.60. 6785-6790 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 根本秀雄: "Olefinic Cyclobutanol Strategy for Halogenated Cyclopentanoids" Tetrahedron Lett.36. 8799-8802 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 根本秀雄: "Cyclobutane Strategy for the Synthesis of A-Ring Aromatic Trichothecanes" Heterocycles. 42. 165-168 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Hideo Nemoto: "A Remarkable Substituent Effect on the Enantioselectivity of Tandem Asymmetric Epoxidation and Enantiospecific Ring Expansion of Cyclopropylidene Alcohols : A New Enantiocontrolled Synthesis of (-)-Debromoaplysin and (-)-Aplysin." J.Org. Chem. 59. 74-79 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Hideo Nemoto: "Tandem Ring Expansion and Insertion Reaction of Alkenic Cyclobutanols Mediated by Palladium-A Novel Approach to Bicyclo [4.3.0] nonane Systems" Tetrahedron. 50. 10391-10396 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Hideo Nemoto: "The First Example of Asymmetric Dihydroxylation of Cyclopropylidene Derivatives-An Enantioenriched Formal Total Synthesis of (-)-Filiformin" Tetrahedron Lett. 36. 1055-1058 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Hideo Nemoto: "A Highly Enantiocontrolled Strategy for the Synthesis of Benzylic Quaternary Carbon Centers. A Formal Total Synthesis of (-)-Mesembrine" J.Org. Chem. 60. 6785-6790 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Hideo Nemoto: "Olefinic Cyclobutanol Strategy for Halogenated Cyclopentanoids" Tetrahedron Lett. 36. 8799-8802 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Hideo Nemoto: "Cyclobutane Strategy for the Synthesis of A-Ring Aromatic Trichothecanes" Heterocycles. 42. 165-168 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 根本英雄: "A Remarkable Substituent Effect on the Enantioselectivity of Tandem Asymmetric Epoxidation and Enantiospecific Ring Expansion of Cyclopropylidene Alcohols : A New Enantiocontrolled Synthesis of(-) -Debromoaplysin and(-) -Aplysin." J. Org. Chem.59. 74-79 (1994)

    • Related Report
      1995 Annual Research Report
  • [Publications] 根本英雄: "Tandem Ring Expansion and Insertion Reaction of Alkenic Cyclobutanols Mediated by Palladium-A Novel Approach to Bicyclo[4. 3. 0]nonane Systems." Tetrahedron. 50. 10391-10396 (1994)

    • Related Report
      1995 Annual Research Report
  • [Publications] 根本英雄: "The First Example of Asymmetric Dihydroxylation of Cyclopropylidene Derivatives-An Enantioenriched Formal Total Synthsis of(-) -Filiformin." Tetrahedron Lett.36. 1055-1058 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 根本英雄: "A Highly Enantiocontrolled Strategy for the Synthesis of Benzylic Quaternary Carbon Centers. A Formal Total Synthesis of(-) -Mesembrine" J. Org. Chem.60. 6785-6790 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 根本英雄: "Olefinic Cyclobutanol Strategy for Halogenated Cyclopentanoids" Tetrahedron Lett.36. 8799-8802 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 根本英雄: "Cyclobutane Strategy for the Synthesis of A-Ring Aromatic Trichothecanes" Heterocycles. 42. 165-168 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] 根本英雄: "A.Rcmarkable Substituent Effect on the Enantioselectivitv of Tandem Asymmetric Epxidation and Enantiospecific Ring Expansion of Cyclopylidene Alsloropylidene Alcohols:A New Enantiocontrolled Synthesis of,(-)Debromoaplysin and(-)-Aplysin." J.Org.Chem.59. 74-79 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 根本英雄: "A Novel Access to Hydrindan Derivatives by Palladium Mediated Tandem Ring Expansion and Insertion Reaction of Alkenic Cyclobutanols." Syn.Lett.599-600 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 根本英雄: "Tandem Ring Expansion and Insertion of Alknic Cyclobutanols Mediated by Palladium--A Novel Approach to Bicyclo〔4.3.0〕nonane Systems." Tetrahedron. 50. 10391-10396 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 根本英雄: "An Asymmetric Synthesis of Benzylic Crabon Centers.A Formal Total Synthesis(-)-Mesembrine" Tetrahedron Lett. 35. 6499-6502 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 根本英雄: "An Efficient Route to Chiral Benzooxabicyclo〔3.2.1〕octane Ring System--The First Enantiocontrolled Total Synthesis of(-)-Filiformin." Heterocycles. 39. 467-470 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 根本英雄: "The First Example of Asymmetric Dihydroxylation of Cyclopylidene Derivatives-An Enanitioenriched Total Synthsis of(-)-Filiformim." Tetrahedron Lett.36. 1055-1058 (1995)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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