• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Research on Asymmetric Reaction with New Chiral Schiff Base-Metal Cpmplexes

Research Project

Project/Area Number 08454202
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionYamaguchi University

Principal Investigator

OGUNI Nobuki  Yamaguchi University, Faculty of Science, Professor., 理学部, 教授 (60028165)

Project Period (FY) 1996 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 1998: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1997: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1996: ¥4,800,000 (Direct Cost: ¥4,800,000)
KeywordsAsymmetric Catalysis / Optically Active Compounds / Chiral Schiff Base / Titanium Complexes / Asymmetric Silylcyanation / Diketene / ASymmetric Ring-Opening Reaction / Phenyllithium / キラルなシッフ塩基 / 不斉シリルシアノ化反応 / フェニルリチウム / β-アミノアルコール / L-バリノール / 不斉とリルシアノ化 / ジメチル亜鉛 / コレステロール低下剤 / chiral titanium complex / chiral glycol of ferrocene / asymmetric alkylation / chiral di-Schiff base
Research Abstract

I already invented many new catalytic enantioselective reactions using chiral schiff base-metal complexes as catalyst. One of them was enantioselective addition of trimethylcyanide to aldehydes to give highly optically active cyanohydrins over 90% ee.
The investigations by this project were new some enantioselective catalysis using chiral schiff bases. The first was the enantioselective addition of diketene to aldehydes to give chiral 5-hydroxy-3-ketoesters. Some kind of the products can be applied for the synthesis of new medicine lowering colesteroles in blood. The use of 10 mo1% of chiral titanium catalyst afforded over 90% ee's product in quantitative chemical yield.
The second research was the enantioselective ring opening arylation of symmetrical epoxides such as cyclohexene oxide. Lithium alokoxide of chiral schiff bases in reaction media acts as catalyst to give ring opening product having over 90% ee. The products easily were recrystallized to give optically pure compounds. Also trans-2-arylcyclohexanols are very useful chiral precursors to prepare a variety of medicines. This invension was applied as a patent.

Report

(4 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • 1996 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] M.Hayashi, K.Ono, H.Hoshimi, N.Oguni,: "Asymmetric ring opening reaction of symmetrical N-Acylaziridines with thiols catalyzed by chiral dialkyl tartrate-diethylzinc complexes." Tetrahedron. 52. 7817-7832 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 小国信樹: "対称化合物の非対称化操作-特に不斉触媒による環状化合物の開環." 有機合成化学協会誌、. 54. 829-835 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Oguni, K.Tanaka, H.Ishida,: "Catalytic enantioselective reaction of diketene with aldehydes catalyzedby chiral schiff base-titanium alkoxide complexes." Synlett. 601-602 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Oguni, Y.Miyagi, K.Itoh,: "Highly enantioselective arylation of symmetrical epoxides with phenyllithium promoted by chiral schiff bases and salens." Tetrahedron Letters,. 39. 9023-9026 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Oguni, N.Satoh,: "Highly enantioselective methylation of 3-trimethylsilylpropanal with dimethylzinc catalyzed by chiral schiff base-titanium complexes." Tetrahedron Letters,. 40(印刷中). (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Oguni (分担執筆): "Metal Catalyzed Addition of Cyanides to Aldehydes. in “Transition metal for Organic Synthesis" Ed. M.Beller, C.Bolm" Wiley-VCH, (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Oguni (分担執筆): "Zinc(II) Reagents. in “Lewis Acid Reagents. A Practical Approach" Ed. H.Yamamoto." Oxford University Press,(1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Hayashi, K.Ono, H.Hoshimi, N.Oguni: "Asymmetric ring opening reaction of symmetrical N-Acylaziridines with thiols catalyzed by chiral dialkyl tartrate-diethylzinc complexes." Tetrahedron. 52. 7817-7832 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Oguni, K.Tanaka, H.Ishida: "Catalytic enantioselective reaction of diketene with aldehydes catalyzedby chiral schiff base-titanium alkoxide complexes." Synlett. 601-601 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Oguni, Y.Miyagi, K.Itoh: "Highly enantioselective arylation of symmetrical epoxides with phenyllithium promoted by chiral schiff bases and salens" Tetrahedron Letters. 39. 9023-9026 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Oguni, N.Satoh: "Highly enantioselective methylation of 3-trimethylsilylpropanal with dimethylzinc catalyzed by chiral schiff base-titanium complexes." Tetrahedron Letters. (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Hayashi,K.Ono,H.Hoshimi,N.Oguni,: "Asymmetric ring opening reaction of symmetrical N-Acylaziridines with thiols catalyzed by chiral dialkyl tartrate-diethylzinc complexes." Tetrahedron. 52. 7817-7832 (1996)

    • Related Report
      1998 Annual Research Report
  • [Publications] 小国信樹: "対称化合物の非対称化操作-特に不斉触媒による環状化合物の開環." 有機合成化学協会誌、. 54. 829-835 (1996)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni,K.Tanak,H.Ishida,: "Catalytic enantioselective reaction of dikatene with aldehydes catalyzedby chiral schiff base-titanium alkoxide complexes." Synlett. 601-602 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni,Y.Miyagi,K.Itoh,: "Highly enantioselective arylation of symmetrical epoxides with phenyllithium promoted by chiral schiff bases and salens." Tetrahedron Letters,. 39. 9023-9026 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni,N.Satoh,: "Highly enantioselective methylation of 3-trimethylsilylpropanal with dimethylzinc catalyzed by chiral schiff base-titanium complexes." Tetrahedron Letters,. 40(印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni: "Metal Catalyzed Addition of Cyanides to Aldehydes.in “Transition metal for Organic Synthesis"Ed.M.Beller,C.Bolm" Wiley-VCH, 6 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni: "Zinc(II)Reagents.in “Lewis Acid Reagents.A Practical Approach"Ed.H.Yamamoto." Oxford University Press,23 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 小国信樹: "キラルなルイス酸触媒反応-特にチタン錯体触媒を中心に-" 化学と工業. 50. 1492-1495 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] N.Oguni and K.Hayashi: "Enantioselective desymmetrization reaction of cyclohexene oxide with primary amines." Synlett.(in press). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] N.Oguni: "Lewis Acid Reagents : A Practical Approach″" Oxford University Press, (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] N.Oguni: "Metal Catalyzed Addition of Cyanide to Aldehydes ″Transition Metals for Fine Chemicals and Organic Synthesis″" VCH Publishers, (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Hayashi,K.Ono,H.Hoshimi,N.Oguni: "Asymmetric ring opening reactions of symmetrical N-acylaziridines with thiols catalyzed by chiral dialkyl tartrate diethylzinc complexes." Tetrahedron. 52巻. 7817-7832 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 小国信樹: "対称化合物の不斉非対称化操作-特に不斉触媒による環状化合物の開環" 有機合成化学協会誌. 54巻10号. 829-835 (1996)

    • Related Report
      1996 Annual Research Report

URL: 

Published: 1996-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi