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DEVELOPMENT OF CATALYTIC ASYMMETRIC REACTIONS USING LANTANOIDS

Research Project

Project/Area Number 13672207
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

NISHIDA Atsushi  CHIBA UNIVERSITY, GRADUATE SCHOOL OF PHARMACEUTICAL SCIENCES, PROFESSOR, 大学院・薬学研究院, 教授 (80130029)

Co-Investigator(Kenkyū-buntansha) ARISAWA Mitsuhiro  CHIBA UNIVERSITY, GRADUATE SCHOOL OF PHARMACEUTICAL SCIENCES, ASSISTANT PROFESSOR, 大学院・薬学研究院, 助手 (40312962)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2002: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2001: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsAsymmetric Diels-Alder reactions / BINAMIDE / Yb(OTf)_3 / sarkomycin / TXA2 antagonist / allylic halogenation / Pictet-Spengler reaction / サルコマイシン / トロンボキサンA_2拮抗剤 / NBS / Fischerインドール合成 / ピロロインドール / シロキシジエン / 軸不斉配位子 / 2,2'-diaminobinaphthalene / 不斉Diels-Alder反応 / Sarkomycin / Yb(Otf)_3 / 閉環メタセシス / Poctet-Spengler反応 / テトラヒドローβ-カルボリン
Research Abstract

1) Asymmetric Diels-Alder reactions of cyclopentadiene and several dienophiles catalyzed by a chiral ytterbium complex prepared by a noble axially asymmetric chiral ligand, BINAMIDE and Yb(OTf)_3 were investigated.
The reaction with bromoacryloyl amide afforded cyclo-adduct in 97% yield with 98% de and with 93% ee. The adduct was converted cyclosarkomycin, a key intermediate for the synthesis of antitumor antibiotics sarkomycin (overall 6%, 10 steps). Although a diastereoselective synthesis of optically active cyclosarkomycin has been reported, this is the first catalytic enentioselective synthesis cyclosarkomycin.
The reaction with a fumaric acid derivative gave a mixture of adduct in 83% yield with 52% de and with 84% ee. The adduct was converted to a key intermediate for the synthesis of TXA2 antagonist, ONO-8809 which was developed by Ono company. This fumaric acid derivative also reacted with siloxydiene to give a cyclohexene derivative with low enantioselectivity (13% ee).
2) A new allylic halogenation and Pictet-Spengler reaction of imines, both catalyzed by Yb(OTf)_3 were developed. Asymmetric version of these reactions will be developed in future.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] Riichiro Tsuji, Masamichi Yamanaka, Atsushi Nishida, Masako Nakagawa: "Pictet-Spengler Reaction of Nitrones and Imines Catalyzed by Yb(OTf)_3-TMSCI"Chem. Lett. 428-429 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masamichi Yamanaka, Mitsuhiro Arisawa, Atsushi Nishida, Masako Nakagawa: "An Intriguing Effect of Yb(OTf)_3-TMSCI in the Halogenation of 1,1-Disubstituted Alkenes by NXS : Selective Synthesis of Allyl Halides"Tetrahedron Lett. 43. 2403-2406 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Mitsuhiro Arisawa, Yuko Ando, Masamichi Yamanaka, Masako Nakagawa, Atsushi Nishida: "Novel Synthetic Method for 2,3-Dihydro-3-halo-3-methylindole from N-Acetyl-2-isopropenylaniline by Intramolecular Haloamination"Synlett. 1514-1516 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Riichiro Tsuji, Atsushi Nishida, Masako Nakagawa: "Simple Synthesis of Racemic Pyrrolo[2,3-b]indoles ; Formal Total Synthesis of (-)-Physostigmine"Heterocycle. 58. 587-593 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Riichiro Tsuji, Masako Nakagawa, Atsushi Nishida: "Efficient Synthetic Approach to Optically Active β-Carboline Derivatives via Pictet-Spengler Reaction Promoted by Trimethylchlorosilane"Tetrahedron Asymmetry. 14. 177-180 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masamichi Yamanaka, Atsushi Nishida, Masako Nakagawa: "Imino Ene Reaction Catalyzed by Ytterbium(III) Triflate and TMSCI or TMSOTf"J. Org. Chem. 68. 3112-3120 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Riichiro Tsuji, Masamichi Yamanaka, Atsushi Nishida, Masako Nakagawa: "Pictet-Spengler Reaction of Nitrones and Imines Catalyzed by Yb(OTf)_3-TMSCl"Chem.Lett.. 428-429 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masamichi Yamanaka, Mitsuhiro Arisawa, Atsushi Nishida, Masako Nakagawa: "An Intriguing Effect of Yb(OTf)_3-TMSCl in the Halogenation of 1,1-Disubstituted Alkenes by NXS : Selective Synthesis of Allyl Halides"Tetrahedron Lett.. 43. 2403-2406 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Mitsuhiro Arisawa, Yuko Ando, Masamichi Yamanaka, Masako Nakagawa, Atsushi Nishida: "Novel Synthetic Method for 2,3-Dihydro-3-halo-3-methylindole from N-Acetyl-2-isopropenylaniline by Intramolecular Haloamination"Synlett. 1514-1516 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Riichiro Tsuji, Atsushi Nishida, Masako Nakagawa: "Simple Synthesis of Racemic Pyrrolo[2,3-b]indoles ; Formal Total Synthesis of (±)-Physostigmine"Heterocycles. 58. 587-593 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Riichiro Tsuji, Masako Nakagawa, Atsushi Nishida: "Efficient Synthetic Approach to Optically Active β-Carboline Derivatives via Pictet-Spengler Reaction Promoted by Trimethylchlorosilane"Tetrahedron Asymmetry. 14. 177-180 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masamichi Yamanaka, Atsushi Nishida, Masako Nakagawa: "Imino Ene Reaction Catalyzed by Ytterbium(III) Triflate and TMSCl or TMSOTf"J. Org.Chem.. 68. 3112-3120 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Riichiro Tsuji, Atsushi Nishida, Masako Nakagawa: "Simple Synthesis of Racemic Pyrrolo[2, 3-b]indoles : Formal Total Synthesis of (±)-Physostigmine"Heterocycles. Vol.58. 4629-4638 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Mitsuhiro Arisawa, Yuko Ando, Masamichi Yamanaka, Masako Nakagawa, Atsushi Nishida: "Novel Synthetic Method for 2,3-Dihydro-3-halo-3-methylindole from N-Acetyl-2-isopropenylaniline by Intramolecular Haloamination"Synlett. No.9. 1514-1516 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Riichiro Tsuji, Masamichi Yamanaka, Atsushi Nishida, Masako Nakagawa: "Pictet-Spengler Reaction of Nitrones and Imines Catalyzed by Yb(Otf)_(3)-TMSCI"Chemistry Letters. (印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Mitsuhiro Arisawa, Kaneko Hiroaki, Atsushi Nishida, Masako Nakagawa: "Stereoselectivity in Ring-Closing Olefin Metathesis (RCM) of Tethered Di-hexenoy1 Derivatives, Mitsuhiro Arisawa"J. Chem. Soc. Perkin Trans 1. (印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Masamichi Yamanaka, Mitsuhiro Arisawa, Atsushi Nishida, Masako Nakagawa: "An Intriguing Effect of Yb(Otf)_(3)-TMSCI in the Halogenation of 1, 1-Disubstituted Alkenes by NXS : Selective Synthesis of Ally1 Halides"Tetrahedron Letters. 43・(印刷中). (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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