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1997 Fiscal Year Final Research Report Summary

Catalytic Asymmetric Synthesis of Bioactive Molecules

Research Project

Project/Area Number 07557139
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Chemical pharmacy
Research InstitutionKYOTO UNIVERSITY (1996-1997)
Osaka University (1995)

Principal Investigator

TOMIOKA Kiyoshi  KYOTO UNIVERSITY Graduate School of Phamaceutical Sciences, Professor, 薬学研究科, 教授 (50114575)

Co-Investigator(Kenkyū-buntansha) INOUE Isao  Tanabe Seiyaku Co., Ltd., Investigator, 研究員
NAGAOKA Yasuo  KYOTO UNIVERSITY Graduate School of Phamaceutical Sciences, Instructor, 薬学研究科, 助手 (90243039)
IIDA Akira  KYOTO UNIVERSITY Graduate School of Phamaceutical Sciences, Assiociate Professor, 薬学研究科, 助教授 (40202816)
Project Period (FY) 1995 – 1997
Keywordschiral ligand / lithiumthiolate / conjugate addition / lithium enolate / catalytic reaction / asymmetric reaction / 2-trimethylsilythiphenol / conjugate addition
Research Abstract

As our continuing studies toward enantioselective reactions of organolithiums based on an external chiral ligand, we have developed the catalytic asymmetric addition of thiophenol to enoates using lithium thiophenolate as a catalytic nucleophile which has higher reactivity than thiophenol activated by amine. The 2-substituent of thiophenol exerts profound effects on reactivity and enantioselectivity in the asymmetric addition reaction with enoates catalyzed by lithium thiophenolate and a chiral ligand. The bulky substituent gave the higher reactivity and enantioselectivity. The asymmetric reaction of 2-trimethylsilylthiophenol with methyl enoates was catalyzed by the combination of 0.08 eq of lithium 2-trimethylsilylthiophenolate and 0.1 eq of the chiral ligand, (1R,2R)-1-dimethylamino-2-(2-methoxyphenoxy)-1,2-diphenylethane, in toluene-hexane (1 : 1) to afford the corresponding methyl 3-(2-trimethylsilylphenylthio) carboxylates in excellently high ees. The chiral ligand was recovered quantitatively for reuse without racemization. The 2-trimethylsilyl group was protodesilylated by treatment with triflic acid to give the corresponding 3-phenylthiocarboxylates in excellently high yield without racemization. The kinetic control is operative in the asymmetric addition reaction.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] Y.Nagaoka: "Structural Requirements of a Chiral Ligand for the Catalytic Asymmetric Addition of Thiophenol to a.b-Unsaturated Esters" Tetrahedron Letters. (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tomioka: "The Asymmetric Horner-Wadsworth-Emmons Reaction Mediated by An External Chiral Ligand" Angewandte.Chemie.37・4. 515-517 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Iida: "The Chiral Ligand Catalyzed Enantioselective Conjugate Addition of Organolithium to BHA Enoates" Chem.Pharm.Bull.46・1. 184-186 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tomioka: "Enantioselective Addition of Thiazolylliithium to Aldimines with the Aid of Chiral Ligand" Heterocycles. 47. 77-78 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Nishimura: "Steric Tuning of Reactivity and Enantioselectivity in Addition of Thiophenol to α.β-Unsaturated Esters Mediated by a Chiral Ligand" J.Am.Chem.Soc.119・52. 12974-12975 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tomioka: "Enantioselective Conjugate Additions of Organolithiums to BHA Enoates Mediated By A Chiral Ligand" Tetrahedron Letters. 38・52. 8973-8976 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kiyoshi Tomioka, Manabu Okuda, Katsumi Nishimura, Shino Manabe, Motomu Kanai, Yasuo Nagaoka, and Kenji Koga: "Structural Requirements of a Chiral Ligand for the Catalytic Asymmetric Addition of Thiophenol to alpha, beta-Unsaturated Esters" Tetrahedron Letters. 39(15). 2141-2144 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masashi Mizuno, Kunihiko Fujii, and Kiyoshi Tomioka: "The Asymmetric Horner-Wadsworth-Emmons Reaction Mediated by An External Chiral Ligand" Angew.Chem.Int.Ed.Engl. 37(4). 515-517 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yasutomi Asano, Akira Iida, and Kiyoshi Tomioka: "The Chiral Ligand Catalyzed Enantioselective Conjugate Addition of Organolithium to BHA Enoates." Chem.Pharm.Bull. 46(1). 184-186 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kiyoshi Tomioka, Maki Satoh, Daisuke Taniyama, Motomu Kanai, and Akira Iida.: "Enantioselective Addition of Thiazolyllithium to Aldimines with the Aid of Chiral Ligand. Asymmetric Syntesis of (S)-Doe.A Component of Marine Natural Product, Dolastatin 10" Heterocycles. 47. 77-81 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Katsumi Nishimura, Takashi Ono, Yasuo Nagaoka, and Kiyoshi Tomioka: "Steric Tuning of Reactivity and Enantioselectivity in Addition of Thiophenol to alpha, beta-Unsaturated Esters Mediated by a Chiral Ligand" J.Am.Chem.Soc.119(52). 12974-12975 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yasutomi Asano, Akira Iida, and Kiyoshi Tomioka: "Enantioselective Conjugate Additions of Organolithiums to BHA Enoates Mediated By A Chiral Ligand" Tetrahedron Letters. 38(52). 8973-8976 (1997)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1999-03-16  

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