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Catalytic asymmetric synthesis of optically active amines and their derivatives

Research Project

Project/Area Number 10640579
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 物質変換
Research InstitutionYamaguchi University

Principal Investigator

HAYASHI Masahiko  Faculty of Science, Yamaguchi University Assistant Professor, 理学部, 助教授 (60192704)

Co-Investigator(Kenkyū-buntansha) 林 昌彦  山口大学, 理学部, 助教授 (60192704)
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1999: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1998: ¥1,700,000 (Direct Cost: ¥1,700,000)
Keywordsasymmetric synthesis / chiral amine / palladium catalyst / allylamine / bidentate ligand / tridentate ligand / Schiff base / titanium complex / 不斉合性 / チタン触媒 / パラジウム錯体 / π-アリル錯体
Research Abstract

For the development of the asymmetric synthesis of optically active amines and their derivatives, we examined the enanioselective addition of trimethylsilyl cyanide to a variety of N-substituted imines. At first, we investigated the reaction catalyzed by chiral Schiff base-titanium alkoxide complexes which was very effective for enantioselective trimethylsilylcyanation of aldehydes. We found that by using chiral titanium complexes, high chemical yield was attained, but only unsatisfied optical yield (20% ee) was obtained. The chiral titanium complex bearing chiral binaphthol derivatives was also found to give only low optical yield. Then we examined the reaction catalyzed by cationic chiral BINAP- palladium complex. By using complex of in-situ preparation and isolated one, low optical yield was obtained in both cases though chemical yield was high. Based on the above results we changed the strategy for the synthesis of optically active amines, that is, catalytic asymmetric allylic amination catalyzed by palladium complexes. We have succeeded in the synthesis of novel palladium catalyst having P, N-bidentate ligands. These new catalyst was found to have high catalytic activity and enantioselectivity in catalytic allylic alkylation. The optical yields of the allylic alkylation products were over 80% ee. At present, the asymmetric amination is being examined.

Report

(3 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] M.Hayashi: "Metal Catalyzed Transfomation of D-Glucal to Optically Active Furan Diol"Chem.Commun.. 965-966 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Hayashi: "Hydrogen Transfer of D-Glycals by Palladium Complexes under Ethylene Atmosphere"Tetrahedron Lett.. 40. 1171-1174 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Hayashi: "C-Glycosydation of Unprotected Glycals with Trimethylsilyl Cyanide"Tetrahedron Lett.. 40. 1729-1730 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Hayashi: "Practical and Catalytic Synthesis of 1,5-Anydrohex-1-en-3-uloses"Tetrahedron. 55. 8331-8340 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Hayashi: "Efficient Synthesis of Carbohydrate-containing Carbocyclic Compounds Based on Palladium-catalyzed Vinylation of Sugars and Subsequent Diels-Alder Reaction"Tetrahedron. 55. 12287-12294 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Hayashi: "Dehydrogenation Reactions by Palladium Supported on Activated Charcoal under Ethylene Atmosphere:Synthesis of 1,5-Anlydrohex-1-en-3-uloses"Synthesis. 1869-1871 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 0.Loiseleur: "Enantioselective Heck Reactions using Chiral P,N-ligands in "Perspective in Organopalladium Chemistry for XXI Century""Elsevier. 7 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Hayashi, H. Kawabata, and K. Yamada: "Metal Catalyzed Transformation of D-Glucal to Optically Active Furan Diol."Chem. Commun.. 965-966 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Hayashi, K. Yamada, and O. Arikita: "Hydrogen Transfer of D-Glycals by Palladium Complexes under Ethylene Atmosphere"Tetrahedron Lett.. 40. 1171-1174 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Hayashi, H. Kawabata, and O. Arikita: "C-Glycosydation of Unprotected Glycals with Trimethylsilyl Cyanide."Tetrahedron Lett.. 40. 1729-1730 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Hayashi, K. Yamada, and O. Arikita: "Practical and Catalytic Synthesis of 1, 5-Anhydrohex-1-en-3-uloses."Tetrahedron. 55. 8331-8340 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Hayashi, K. Tsukada, H. Kawabata, and C. Lamberth: "Efficient Synthesis of Carbohydrate-containing Carbocyclic Compounds Based on Palladium-catalyzed Vinylation of Sugars and Subsequent Diels-Alder Reaction."Tetrahedron. 55. 12287-12294 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Hayashi, K. Tsukada, K. Amano, and C. Lamberth: "Efficient Synthesis of Branced-chain Sugars in Aqueous Media by Heck-type Reaction."J. Chem. Soc., Perkin 1. 239-240 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Hayashi, K. Yamada, and S. Nakayama: "Dehydrogenation Reactions by Palladium Supported on Activated Charcoal under Ethylene Atmosphere : Synthesis of 1, 5-Anhydrohex-1-en-3-uloses."Synthesis. 1869-1871 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] O. Loiseleur, M. Hayashi, M. Keenan, N. Schmees, and A. Pfaltz: "Enantioselective Heck Reactions using Chiral P, N-ligands."J. Organomet. Chem.. 576. 16-22 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Hayashi, H. Kawabata, and K. Inoue: "Thermal C-Glycosidation of Protected and Unprotected D-Glucal."Carbohydrate Res.. 325. 68-71 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Hayashi, H. Kawabata, S. Shimono, and A. Kakehi: "Palladium-catalyzed Stereoselective C-Glycosidation of Unprotected Enones Derived from D-Glucal with Trimethylsilyl Cyanide."Tetrahedron Letters. in press. (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] O. Loiseleur, M. Hayashi, M. Keenan, N. Schmees, and A. Pfaltz: "Enantioselective Heck Reactions using Chiral P, N-ligands, in "Perspective in Organopalladium Chemistry for XXI Century". J. Tsuji, Ed."Elsevier. 16-22 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Hayashi: "Metal Catalyzed Transformation of D-Glucal to Optically Active Furan Diol"Chem.Commun.. 965-966 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Hayashi: "Hydrogen Transfer of D-Glycals by Palladium Complexes under Ethylene Atmosphere"Tetrahedron Lett.. 40. 1171-1174 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Hayashi: "C-Glycosydation of Unprotected Glycals with Trimethlsilyl Cyanide"Tetrahedron Lett.. 40. 1729-1730 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Hayashi: "Efficient Synthesis of Carbohydrate-containing Carbocyclic Compounds Based on Palladium-catalyzed Vinylation of Sugars and Subsequent Diels-Alder Reaction"Tetrahedron. 55. 12287-12294 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Hayashi: "Practical and Catalytic Synthesis of 1,5-Anhydrohex-1-en-3-uloses"Tetrahedron. 55. 8331-8340 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Hayashi: "Dehydrogenation Reactions by Palladium Supported on Activated Charcoal under Ethylene Atmosphere: Synthesis of 1,5-Anhydrohex-1-en-3-uloses"Synthesis. 1869-1871 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] O.Loiseleur: "Enantioselective Heck Reactions using Chiral P,N-ligands in "Perspective in Organopalladium Chemistry for XXI Century""Elsevier. 7 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Hayashi: "Hydrogen Transfer of D-Glycals by Palladium Complexes under Ethylene Atmosphere" Tetrahedron Letters. 40. 1171-1174 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Hayashi: "C-Glycosidation of Unprotected Glycals with Trimethylsilyl Cyanide" Tetrahedron Letters. 40. 1729-1730 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Hayashi: "Efficient Synthesis of Branched-chain Sugars in Aqueous Media by HecR-type Reaction" J.Chem.Soc.,Perkin Trans 1. 239-240 (1999)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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