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1997 Fiscal Year Final Research Report Summary

New Method for Asymmetric Synthesis by Using Chiral Bases

Research Project

Project/Area Number 08557122
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Chemical pharmacy
Research InstitutionThe University of Tokyo

Principal Investigator

KOGA Kenji  The University of Tokyo, Graduate School of Pharmaceutical Sciences, Professor, 大学院・薬学系研究科, 教授 (10012600)

Co-Investigator(Kenkyū-buntansha) YASUDA Kosuke  Tanabe Seiyaku Co., Ltd., Lead Optimization Research Laboratory, Researcher, 研究員
AOKI Kazumasa  The University of Tokyo, Graduate School of Pharmaceutical Sciences, Assistant, 大学院・薬学系研究科, 助手 (60282612)
SHINDO Mitsuru  The University of Tokyo, Graduate School of Pharmaceutical Sciences, Assistant, 大学院・薬学系研究科, 助手 (40226345)
ODASHIMA Kazunori  The University of Tokyo, Graduate School of Pharmaceutical Sciences, Associate P, 大学院・薬学系研究科, 助教授 (30152507)
Project Period (FY) 1996 – 1997
Keywordslithium enolate / asymmetric synthesis / catalytic asymmetric synthesis / deprotonation / alkylation / protonation / Michael reaction / chiral amine
Research Abstract

Enantioselctive synthesis and reactions of enolate ions are one of the important area in modern synthetic chemistry. The aim of this project is the design and synthesis of multidentate-type chiral lithium amides and the corresponding chiral amines, their applications to the enantioselective synthesis of chiral lithium enolates and to the enantioselective reactions of prochiral lithium enolates, and the development of these reactions to highly catalytic systems. We obtained the following results through this project.
(1) The combination of a catalytic amount of a chiral amine and a stoichiometric amount of an achiral lithium amide has realized catalytic asymmetric deprotonation reactions of prochiral ketones.
(2) The new C_2 symmetric chiral tetraamine has been found to be an excellent ligand for catalytic asymmetric alkylation of lithium enolates derived from alpha, alpha-disubstituted ketones.
(3) Catalytic asymmetric protonation of prochiral ketones has been realized by using a catalytic amount of chiral tetraamine and a proton source which is hardly soluble in the solvent used.
(4) Enantioselective Michael reactions of acyclic ketones have been realized by using a chiral tetraamine.

  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] K.Yasuda.: "Enantioselective miael reaction of ketone enolates using chiral amine ligamine ligand." Tetrahedron Lett.37. 6343-6346 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Sugasawa.: "Solution suructures of a monodentate chiral lithium amede in the presence of lithium halide." Tetrahedron Lett.37. 7377-7380 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Yamashita.: "An approach to Catalytic asymmetric deprotonation of 4-substituted cyclohexanones." Tetrahedron Lett.37. 8195-8198 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Ishii.: "Enantioselective methylation of the lithium enolate of 1-tetralone mediatde by chiral C_2-summetric DMEU derevatives." Tetrahedron Lett.38. 563-566 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Toreyama.: "Stereochemistry of enantioselective deprotonation of 4-substituted cyclohexanones by chiral bidentate lithium amides." Tetrahedron Lett.38. 567-570 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Aoki.: "Enantioselective deprotonation of 4-tert-butylcyclo hexanone by pluorine-cotaining chiral lithium amides dereved fromt α-phenethylamine." Tetrahedron Lett.38. 2505-2506 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Kumamoto.: "Enantioselective horner-wadsworth-emmons reaction using chiral lithium 2-aminoalkoxides." Chem.Pharm.Bull.45. 753-755 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Yasuda.: "Cmstrucion of Contiguous chiral tertiary centers by enanhoselective michael reachon of kehme lithium enolates using a chival amino ligand.." Tetrahedron Lett.38. 7589-7592 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] P.Riviere.: "An approach to catalytic enantioselective prorsnation of prochiral lithium enolates." Tetrahedron Lett.38. 7589-7592 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Chatani: "Chiral bideatate lithium amides Hving a chiral amide nirtogen for enantioselective deprotomation of 4-tert-butylcyclohexanone." Heterocyclse.46. 53-56 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] J.Matuo.: "Enantioselective α-albylation of phenylacatic acid using a chiral bidentate lithium amide as a chiral auxiliary." Chem.Pharm.Bull.45. 2122-2124 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 古賀 憲司: "キラル塩基を用いる不斉合成" 薬学雑誌. 117. 800-816 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Yasuda: "Enantioselective Michael Reaction of Ketone Lithium Enolates Using Chiral Amine Ligand." Tetrahedron Lett.37. 6343-6 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Sugasawa: "Solution structures of a Monodentate Chiral Lithium Amide in the Presence of Lithium Halide." Tetrahedron Lett.37. 7377-80 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Yamashita: "An Approach to Catalytic Asymmetric Deprotonation of 4-Substituted Cyclohexanones." Tetrahedron Lett.37. 8195-8 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Ishii: "Enantioselective Methylation of the Lithium Enolate of 1-Tetralone Mediated by Chiral C_2-Symmetric DMEU Derivatives." Tetrahedron Lett.38. 563-6 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Toriyama: "Stereochemistry of Enantioselective Deprotonation of 4-Substituted Cyclohexanones by Chiral Bidentate Lithium Amides." Tetrahedron Lett.38. 567-70 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Aoki: "Enantioselective Deprotonation of 4-tert-Butylcyclohexanone by Fluorine-Containing Chiral Lithium Amides Derived from alpha-Phenethylamine." Tetrahedron Lett.38. 2505-6 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Kumamoto: "Enantioselective Horner-Wadsworth-Emmons Reaction Using Chiral Lithium 2-Aminoalkoxides." Chem.Pharm.Bull.45. 753-5 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Yasuda: "Construction of contiguous Chiral Tertiary Carbon Centers by Enantioselective Michael Reaction of Ketone Lithium Enolates Using a Chiral Amine Ligand." Tetrahedron Lett.38. 3531-4 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] P.Riviere: "An Approach to Catalytic Enantioselective Protonation of Prochiral Lithium Enolates." Tetrahedron Lett.38. 7589-92 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Chatani: "Chiral Bidentate Lithium Amides Having a Chiral Amide Nitrogen for Enantioselective Deprotonation of 4-tert-Butylcyclohexanone." Heterocycles. 46. 53-6 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] J.Matsuo: "Enantioselective alpha-Alkylation of Phenylacetic Acid Using a Chiral Bidentate Lithium Amide as a Chiral Auxiliary." Chem.Pharm.Bull.45. 2122-4 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Koga: "Asymmetric Synthesis using Chiral Bases." Yakugaku Zasshi. 117. 800-816 (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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