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Development of Highly Stereoselective Reaction in Metal and Hetero-Atom Combined Reaction Filed

Research Project

Project/Area Number 04453098
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

UTIMOTO Kiitiro  Kyoto University, Material Chemistry, Professor, 工学部, 教授 (90025958)

Co-Investigator(Kenkyū-buntansha) MATSUBARA Seijiro  Kyoto University, Material Chemistry, Instructor, 工学部, 助手 (90190496)
OSHIMA Koichiro  Kyoto University, Material Chemistry, Professor, 工学部, 教授 (00111922)
Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥7,100,000 (Direct Cost: ¥7,100,000)
Fiscal Year 1993: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 1992: ¥4,400,000 (Direct Cost: ¥4,400,000)
KeywordsLanthonoids Reagent / Diastereoselectivity / Optically Active Amine / 1,4-Addition / beta-Keto Amide / Organomanganese Reagent / β-ケトアミド / 有機マンガン反応剤 / 1,4付加 / 光学活性アルコール / オキサチアン化合物 / βーケトアミド / カルシウム反応剤
Research Abstract

(1) An addition of various organolithium compounds to imine or hydrazine derived from optically active 2-formy1-1,3-oxathiane gave amine derivatives with high diastereoselectivity (>99% de) in good yields.
(2) Diastereoselective 1,4-addition reaction of optically active 2-butenoy1-1,3-oxathiane was studied. The addition of organocupper reagent in the presence of YbCl_3 provided 1,4-adduct as a single diastercomeric compound. On the other hand, treatment with organomagnesium reagent in the presence of a catalytic amount of CuBr gave the other diastereomer with high diastereoselectivity.
(3) Lanthanoid triflate proved to be a good catalyst for the 1,4-addition reaction of various amines to alpha, beta-unsaturated esters. The reaction was succesfully applied to a diastereoselective synthesis of optically active beta-lactams.
(4) Stereoselective alkylation of 2-alky1-2-formylamide with alky1-aluminium dichloride was achieved. An addition of trialkylaluminium or alkylmanganese chloride to 2-methy1-3-oxo-amide gave the corresponding 3-hydroxy-2-methylamide with high stereoselectivity.

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] 内本喜一朗: "有機金属化合物を用いる高選択的有機反応" 有機合成化学協会誌. 51. 1064-1073 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Toshiaki YOKOO: "Ytterbium Catalyzed Oxidation of Alcohols to Aldehydes and Ketones by Means of Iodosylbenzene" Chemistry Letters. 571-572 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Masahiko TANIGUCHI: "Stereoselective Reduction of 2-Methyl-3-oxo Esters(or Amides)with Sodium Borohydride Catalyzed by Magnesium Chroride or Tetrabutylammonium Borohydrides.A Practical Preparation of erythro and threo-3-Hydroxy-2-methylEsters(or Amides)" Tetrahedron. 49. 11169-11182 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Seijiro MATSUBARA: "Lanthanoid Triflate Catalyzed Conjugate Addition of Amines to α,β-Unsaturated Esters.A Facile Route to Optically Active β-Lactum" Chemistry Letters. (印刷中). (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Seijiro MATSUBARA: "Diastereoselective Addtion of Organometallic Reagents to Imines or Hydrazones Containing 1,3-Oxathiane As a Chiral Template" Chemistry Letters. (印刷中). (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Seijiro MATSUBARA: "Alkykidenation of Ketones by gem-Dibromoalkane and Diiodosamarium in the Presence of Chromium(II)Chloride." Chemistry Letters. (投稿準備中). (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiitiro UTIMOTO: "Highly Selective Reactions Using Organometallic Reagents" J.Synthetic Organic Chemistry Japan. Vol.51. 1064-1073 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Tosiali YOKOO, Koichiro OSHIMA, and Kiitoro Utimoto: "Ytterbium Catalyzed Oxidation of Alcohols to Aldehydes and Ketones by Means of lodosylbenzene" Chemistry Letters. 571-572 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Masahiko TANIGUCHI, Hideaki FUJII, Koichiro OSHIMA, and Kiitiro UTIMOTO: "Stereoselective Reduction of 2-Methyl-3-oxo Esters(or Amides)with Sodium Borohydride Catalyzed by Magnesium Chroride or Tetrabutylammonium Borohydrides. A Practical Preparation of erythro and threo-3-Hydroxy-2-methylEsters(or Amides)" Tetrahedron. Vol.49. 11169-11182 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Seijiro MATSUBARA, Masahito YOSHIOKA, and Kiitiro UTIMOTO: "Lanthanoid Triflate Catalyzed Conjugate Addition of amines to alpha, beta-Unsaturated Esters. A Facile Route to Optically Active beta-Lactum" Chemistry Letters. (in Press). (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Seijiro MATSUBARA, Tomohiro KODAMA, Hideo UKITA, and Kiitiro UTIMOTO: "Diastereoselective Addtion of Organometallic Reagents to Imines or Hydrazones Containing 1,3-Oxathiane As a Chiral Template" Chemistry Letters. (in Press). (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Seijiro MATSUBARA, Miyuki HORIUCHI, Kazuhiko TAKAI, and Kiitiro UTIMOTO: "Alkykidenation of Ketones by gem-Dibromoalkane and Diiodosamarium in the Presence of Chromium(II)Chloride." Chemistry Letters. (To be published).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 内本喜一朗: "有機金属化合物を用いる高選択的有機反応" 有機合成化学協会誌. 51. 1064-1073 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Toshiaki YOKOO: "Ytterbium Catalyzed Oxidation of Alcohols tp Aldehydes and Ketones by Means of Iodoaldejydes" Chemistry Letters. 571-572 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Masahiko TANIGUCHI: "Stereoselective Reduction of 2-Methyl-3-oxo Esters(or Amides)with Sodium Borohydride Catalyzed by Magnesium Choride or Tetrabutylammonium Borohydride.A Practical Preparation of erythro and threo-3-Hydroxy-2-methyl Esters(or Amides)" Tetrahedron. 49. 11169-11182 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Seijiro MATSUBARA: "Lanthanoid Triflate Catalyzed Conjugated Addition of Amines to α,β-Unsaturated Esters.A Facile Route to Optically Active β-Lactam" Chemistry Letters. (印刷中). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Seijiro MATSUBARA: "Diastereoselective Addition of Organometallic Reagents to Imines or Hydrazones Containing 1,3-Oxathiane As a Chiral Template" Chemistry Letters. (印刷中). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Seijiro MATSUBARA: "Stereocontrolled Reduction of 2‐Acyl‐1,3‐oxathiane Derivatives by Zn(BH_4)_2and YCl_3ーNaBH_4" Chemistry Letters. 2173-2176 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hideaki FUJII: "Stereoselective Addition of Alkyl‐or Phenylaluminum Dichlouide to α‐Alkyl‐β‐hydroxy Amides" Tetrahedron Letters. 33. 4579-4580 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Masahiko TANIGUCHI: "Stereoselective Addition of Organoaluminum or Organomanganese Reagents to 2‐Methyl‐3-oxo Amides(or Esters)Provideing erythro or threo 2‐Mithyl‐3hydroxy Amides(or Esters)" Tetrahedron Letters. 33. 4353-4356 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2017-10-06  

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