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Asymmetric Reactions Catalyzed by Fluorous Chiral Catalysts

Research Project

Project/Area Number 11640548
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionNiigata College of Pharmacy

Principal Investigator

TAKEUCHI Seiji  Niigata College of Pharmacy, Pharmacy, Professor, 薬学部, 教授 (00131011)

Co-Investigator(Kenkyū-buntansha) NAKAMURA Yutaka  Niigata College of Pharmacy, Pharmacy, Research Associate, 薬学部, 助手 (20267652)
Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 2001: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2000: ¥200,000 (Direct Cost: ¥200,000)
Fiscal Year 1999: ¥3,200,000 (Direct Cost: ¥3,200,000)
Keywordsfluorous chiral catalyst / fluorous chiral ligand / asymmetric reaction / recycling of chiral ligand / recycling of chiral catalyst / フルオラスキラルBINAP / 不斉Heck反応 / 安定フルオラスタグ / 触媒 / 不斉合成 / 配位子のリサイクル / フルオラス二相系反応 / CD検出器付きHPLC
Research Abstract

We prepared chiral BINOLs (F_<13>BINOL and F_<17>BINOL), BNAP and ephedrine derivatives which bear long fluorous tags, and also a FiaBINOL derivative the hydroxyl groups of which are (S)-1-phenyl-1-hydroxylethylated (FDHPEB). The BINOLs were easily recovered by using a fluorous reverse phase silica gel (FRP) in a BINOL-Ti complex catalyzed asymmetric addtion reaction of Et2Zn to aldehydes and were reused without further purification to give similar enantioselectivities to the original non-fluorous reaction. The chiral fluorous catalyst in the fluorous phase was reused at least 5 times to give similar enantioselectivities to the original one in a toluene/FC-72 biphasic system. FDHPEB was also reused with the use of the FRP silica gel in SmI2 mediated reductive cleavage of 1-methoxy-1-phenylcyclohexanone followed by an asymmetric protonation by FDHPEB. After separation of the organic product by FRP silica gel, the crude product was analyzed by a chiral column HPLC with CD detector. Only two peaks due to the enantiomers of the product were observed and> the data revealed that the enantioselectivity was much higher (95 % ee) man that'of the sample which was obtained by purification with a preparative TLC (88 % ee). The results demonstrated that racemization occured to some extent during the purification. Thus the fluorous chiral ligands and catalysts are recyclable with the use of the FRP silica gel or in a fluorous/organic biphase system and the easy separation of the organic product allowed us to perform a quick analysis using HPLC with CD detector.

Report

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

Research Products

(15 results)

All Other

All Publications (15 results)

  • [Publications] Yutaka Nakamura, Seiji Takeuchi: "Asymmetric alkylation of aromatic aldehydes with diethylzinc catalyzed by a fluorous BINOL-Ti complex in an organic and fluorous biphase system"Tetrahedron Letters. 41. 57-60 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Yutaka Nakamura, Seiji Takeuchi: "Preparation of a Fluorous Chiral BINOL Derivative and Application to an Asymmetric Protonation Reaction"Tetrahedron. 56. 351-356 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Yutaka Nakamura, Seiji Takeuchi: "Enantioselective addition of diethylzinc to aldehydes catalyzed by β-aminoalcohols"Tetrahedron. 57. 5565-5571 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Yutaka Nakamura, Seiji Takeuchi: "Recyclable Fluorous Chiral Ligands and Catalysts -Asymmetric Addition of Diethylzmc to Aromatic Aldehydes Catalyzed by Fluorous BINOL-Ti Complexes"Tetrahedron. 58(in press). (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Yutaka Nakamura, Seiji Takeuchi: "Preparation of a Fluorous Chiral BINAP and Application to an Asymmetric Heck Reaction"Tetrahedron Letters. 43(in press). (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Nakamura,Yutaka, Takeuchi,Seiji: "Asymmetric alkylation of aromatic aldehydes with diethylzinc catalyzed by a fluorous BINOL-Ti complex in an organic and fluorous biphase system"Tetrahedron Letters. 41. 57-60 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Nakamura,Yutaka, Takeuchi,Seiji: "Preparation of a Fluorous Chiral BINOL Derivative and Application to an Asymmetric Protonation Reaction"Tetrahedron. 56. 351-356 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Nakamura,Yutaka, Takeuchi,Seiji: "Enantioselective addition of diethylzinc to aldehydes catalyzed by β-aminoalcohols"Tetrahedron. 57. 5565-5571 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Nakamura,Yutaka, Takeuchi,Seiji: "Recyclable Fluorous Chiral Ligands and Catalysts Asymmetric Addition of Diethylzinc to Aromatic Aldehydes Catalyzed by Fluorous BINOL-Ti Complexes"Tetrahedron. 58 (in press). (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Nakamura,Yutaka, Takeuchi,Seiji: "Preparation of Fluorous Chiral BINAP and Application to an Asymmetric Heck Reaction"Tetrahedron Letters. 43 (in press). (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Yutaka Nakamura, Seiji Takeuchi: "Enantioselective addition of diethylzinc to aldehydes catalyzed by fluorous β-aminoalcohols"Tetrahedron. 57・26. 5565-5571 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yutaka Nakamura, Seiji Takeuchi: "Recyclable Fluorous Chiral Ligands and Catalysts"Tetrahedron. 58・(in press). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yutaka Nakamura, Seiji Takeuchi: "Preparation of a Fluorous Chiral BINAP and Application to an Asymmetric Heck Reaction"Tetrahedron Letters. 43・(in press). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Nakamura,S.Takeuchi,Y.Ohgo and D.P.Curran: "Asymmetric alkylation of aromatic aldehydes with diethylzinc catalyzed by a fluorous BINOL-Ti complex in an organic/fluorous bi"Tetrahedron Letters. 41・1. 57-60 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y.Nakamura,S.Takeuchi,Y.Ohgo and D.P.Curran: "Preparation of a Fluorous Chiral BINOL Derivative and Application to an Asymmetric Protonation Reaction"Tetrahedron. 56・3. 351-356 (2000)

    • Related Report
      1999 Annual Research Report

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Published: 1999-03-31   Modified: 2016-04-21  

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