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Asymmetric Synthesis with Chiral Nucleophilc Catalysts

Research Project

Project/Area Number 11470468
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

KAWABATA Takeo  Kyoto University, Institute for Chemical Research, Associate Professor, 化学研究所, 助教授 (50214680)

Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥11,300,000 (Direct Cost: ¥11,300,000)
Fiscal Year 2001: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2000: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 1999: ¥5,100,000 (Direct Cost: ¥5,100,000)
Keywordsnucleophilic catalyst / kinetic resolution / hydrogen bonding / substrate-specificity / acceleration / π-π interaction / meso-diol / proline / 求核触媒 / ペプチド / ラクトン化 / induced fit / プロリン / ヒドロキシプロリン / アミノアルコール / PPY / DMAP
Research Abstract

A chiral nucleophilic catalyst, 4-pyrrolidinopyridine (PPY) analogue, has been developed which could effectively catalyze the acylative kinetic resolution racemic amino alcohol derivatives with selectivity factors of 10 to 54. Kinetic studies of acylation indicated that the observed high enantioselectivity of the acylation promoted by the catalyst is due to the rate acceleration of acylation of one enantiomer rather than the rate deceleration of the other. The origin of the acceleration was revealed to be due to the transition state-hydrogen bonding between a substrate and the catalyst.
Chiral PPY analogues were also readily prepared from L-proline. Although these catalysts do not possess chiral elements near the catalytically active pyridine-nitrogen, they promote kinetic resolution of racemic alcohols highly selectively. Contrary to the mechanism of enantioselective acylation by the previously PPY analogue, π-π interaction between an aromatic ring and pyridinium π-system is critical in the chiral nucleophilic catalysts derived from L-proline. A new generation of chiral nucleophilic catalysts with dual functional side chains was successfully prepared from 4-hydroxy-L-proline. These catalysts showed superior chemo- and enantioselectivity in asymmetric desymmetrization of meso-diols.

Report

(4 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (18 results)

All Other

All Publications (18 results)

  • [Publications] Takeo Kawabata: "Remote Chirality Transfer in Nucleophilic Catalysis with N-(4-Pyridinyl)-L-Proline Derivatives"Chirality. 15・1. 71-76 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Takeo Kawabata: "Preparation and Properties of Chiral 4-Pyrrolidinopyridine (PPY) Analogues with Dual Functional Side Chains"Tetrahedron Letters. 44・8. 1545-1548 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 川端猛夫: "求核触媒を用いる合成反応:不斉合成から基質特異的反応、多成分連続反応に向けて"有機合成化学協会誌. 59・5. 458-459 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 川端猛夫: "エナンチオマーを分別する人工酵素"Bio Industry. 18・8. 16-24 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Takeo Kawabata: "Kinetic Resolution of Amino Alcohol Derivatives with a Chiral Nucleophilic Catalyst : Ascess to Enanatiopure cis-Cyclic Amino Alcohols"Chem. Comm.. 2700-2701 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 川端猛夫: "最新酵素利用技術と応用展開"シーエムシー. 71-81 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kawabata, R. Stragies, T. Fukaya, Y. Nagaoka, H. Schedel, K. Fuji: "Preparation and Properties of Chiral 4-Pyrrolidinopyridine (PPY) Analogues with Dual Functional Side Chains"Tetrahedon Lett.. 44. 1545-1548 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kawabata, R. Stragies, T. Fukaya, K. Fuji: "Remote Chirality Transfer in Nucleophilic Catalysis with N-(4-Pyridinyl)-L-Proline Derivatives"Chirality. 15. 71-76 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kawabata: "Discrimination of Enantiomers by an Artificial Enzyme"Bio Industry. 18. 17-24 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kawabata: "Nucleophilic Catalysis : Asymmetric Synthesis, Substrate-Specific Reactions and Multi-Component Sequential Reactions"J. Syn. Org. Chem. Jpn.. 59. 458-459 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kawabata, K. Yamamoto, Y. Momose, H. Yoshida, Y. Nagaoka, K. Fuji: "Kinetic Resolution of Amino Alcohol Derivatives with a Chiral Nucleophilic Catalyst : Ascess to Enanatiopure cis-Cyclic Amino Alcohols"Chem. Comm.. 2700-2701 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kawabata: "Discrimination of Enantiomers by an Antificial Enzyme"Advanced Enzyme-based Techniques with Comprehensive Applications ; M. Aizawa : Ed.. (CMC, Tokyo). 71-81 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Takeo Kawabata: "Kinetic resolution of amino alcohol derivatives with a chiral nucleophilic catalyst : access to enantiopure cyclic cis-amino alcohols"Chem. Commun.. 2700-2701 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Trusar D.Bagul: "Total Synthesis of Spirotryprostatin B via Asymmetric Nitroolefination"Org. Lett.. 4・2. 249-251 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Takeo Kawabata: "Enantioselective α-allytation of a phenylalanine derivative under the control of aggregation of a chiral nonracemic enolate"Tetrahedron Lett.. 43・8. 1465-1467 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 川端猛夫: "エナンチオマーを分別する人工酵素"Bio Review. 18・8. 16-24 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 川端猛夫: "求核触媒を用いる合成反応:不斉合成から基質特異的反応、多成分連続反応へ向けて"有機合成化学協会誌. 59・5. 52-53 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 川端猛夫: "最新酵素利用技術と応用展開"シーエムシー. 11 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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