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Innovative Structure Conversion of Optically Active Amino Acids by Electrochemical Oxidation and Its Utilization in Organic Synthesis

Research Project

Project/Area Number 09450335
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionKYUSHU UNIVERSITY (1998-1999)
Nagasaki University (1997)

Principal Investigator

MATSUMURA Yoshihiro  Kyushu University, Institute for Fundamental Research of Organic Chemistry, Professor, 有機化学基礎研究センター, 教授 (60026309)

Co-Investigator(Kenkyū-buntansha) 真木 俊英  長崎大学, 薬学部, 助手 (10291535)
木下 敏夫  長崎大学, 薬学部, 助教授 (60039641)
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥13,100,000 (Direct Cost: ¥13,100,000)
Fiscal Year 1999: ¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1998: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1997: ¥8,600,000 (Direct Cost: ¥8,600,000)
KeywordsElectrochemical oxidation / Optical activity / α-Amino acid / Hofmann rearrangement / Alkylation / Memory of chirality / 不斉合成 / 選択性 / カルバメート / 炭素間結合形成 / シクロプロパン化
Research Abstract

Synthesis of optically pure organic compounds is one of topics in current organic synthesis. In this study, electrochemical oxidation was used as a key step for the transformation of easily available α-amino acids to new optically active intermediates, which were further elaborated in organic synthesis as described below.
(1) L-Protein and L-lysine derivatives were converted to optically active α-alkylproline and α-alkylpipecolinic acid derivatives by using electrochemical oxidation as a key step. (2) Optically active acyclic ω-carboxyl-α-alkyl-α-amino acids and new optically active auxiliary were prepared through oxidation products that were prepared by electrochemical oxidation of L-lysine derivative. (3) Optically active β-amino acid (d-threo-methylphenidate) was prepared with a high enantioselectivity by the carbon-carbon bond formation between a-methoxypiperidine derivative and N-phenylacetyloxazolidinone prepared from L-valine. (4) A new reaction condition appropriate to the Hofmann rearrangement was exploited. The reaction condition was created by using an electrochemical method in which 2,2,2-trifluoroethanol (TFEOH) was used as a solvent. Under the reaction condition, L-Glutamine ester derivative was efficiently converted to 2,4-diaminobutyric acid ester without a loss of the original optical purity. Furthermore, tirflouroethoxycarbonylamines, the Hofmann rearrangement products in TFEOH, were found to be precursors for unsymmetrical ureas. (5) Memory of chirality was observed in the non-Kolbe reaction of some kinds of optically active cyclic α-amino acids. (6) An efficient reagent for the Cα-Cβ bond of cyclic amino compounds was exploited and it was applied to the ring opening of L-pipecolinic acid derivative.

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] Y. Matsumura: "New Synthetic Method of Optically Active a-Methylproline and a-Methylpipecolinic Acid using Electrochemical Oxidation as a Key Reaction"Tetrahedron Lett.. 37. 8395-8398 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Matsumura: "Diastereoselective Cyclopropanation Utilizing a New Chiral N, O-Acetals Prepared by Electrochemical Oxidation of Carbamates"J. Chin. Chem. Soc.. 45. 297-302 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Matsumura: "A Convenient Method for Synthesis of Enantiomerically Enriched Methylphenidate from N-Methoxycarbonylpiperidine"Org. Lett. 1. 175-178 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Matsumura: "New reaction conditions using trifluoroethanol for the E-I Hofmann rearrangement"J. Chem. Soc. Perkin Trans. 1. (15). 2057-2060 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Matsumura: "The Electrochemically Induced Hofmann Rearrangement and Its Comparsion weith the Classic Hofmann Rearrangement"Electrochim. Acta. 45(印刷中). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Matsumura: "A New Method for Synthesis of Unsymmetrical Ureas Using Electrochemically Prepared Trifluoroethyl Carbamates"J. Org. Chem.. 65(印刷中). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y, Matsumura: "New Synthetic Method of Optically Active α-Methylproline and α-Methylpipecolinic Acid using Electrochemical Oxidation as a Key Reaction"Tetrahedron Lett.. 37(46). 8395-8398 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y, Matsumura: "Diastereoselective Cyclopropanation Utilizing a New Chiral N, O-Acetals Prepared by Electrochemical Oxidation of Carbamates"J. Chin. Chem. Soc.. 45(2). 297-302 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y, Matsumura: "A Convenient Method for Synthesis of Enantiomerically Enriched Methylphenidate from N-Methoxycarbonylpiperidine"Otg. Lett.. 1(2). 175-178 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y, Matsumura: "New reaction conditions using trifluoroethanol for the E-I Hofmann rearrangement"J. Chem. Soc. Perkin. Trans.. 1(15). 2057-2060 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y, Matsumura: "The Electrochemically Induced Hofmann Rearrangement and Its Comparison with the Classic Hofmann Rearrangement"Electrochem. Acta.. 45(in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y, Matsumura: "A New Method for Synthesis of Unsymmetrical Ureas Using Electrochemically Prepared Trifluoroethyl Carbamates"J. Org. Chem.. 65(in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y.Matsumura: "A Conventient Method of Synthesis of Enantiomerically Enriched Methyl-phenidate from N-Methoxycarbonylpiperidine"Org.Lett.. 1巻2号. 175-178 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y.Matsumura: "New reaction conditions using trifluoroethanol for the E-I Hofmann rearrrangement"J,Chem,Soc,Perkin Trans,1. 15号. 2057-2060 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y.Matsumura: "The Electrochemically Induced Hofmann Rearrangement and Its Comparison with the Classic-Hormann Rearrangement"Electrochim,Acta. 45(印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y.Matsumura: "A New Method for Synthesis of Unsymmetrical Ureas Using Electrochemicaly Prepared Trifluoroethyl Carbamates"J,Org.Chem.. 65(印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y.Matsumura: "Diastereoselective Cyclopropanation Utilizing a New Chiral N,O-Acetals Prepared by Electrochemical Oxidation of Carbamates" J.Chin.Chem.Soc.45巻2号. 297-302 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Matsumura: "New Synthetic Method of Optically Active α-Methylproline and α-Methylpipecolinic Acid using Electrochemical Oxidation as a key Reaction" Tetrahedron Letters. 37(46). 8395-8398 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Matsumura: "Diastereoselective Cyclopropanation Using a New chiral N,O-Acetals Prepared by Electrochemical Oxidation of Carbamates" J.Chin.Chem.Soc.(in press). (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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