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

ASYMMETRIC ALLYLATION REACTION OF IMINES WITH CHIRALLY MODIFIED ALLYLMETALS

Research Project

Project/Area Number 09650955
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionTOYOHASHI UNIVERSITY OF TECHNOLOGY

Principal Investigator

ITSUNO Shinichi  Toyohashi University of Technology, Associate Professor, 工学部, 助教授 (50158755)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 1998: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1997: ¥2,300,000 (Direct Cost: ¥2,300,000)
KeywordsEnantioselective addition / N-Metallo imine / N-Masked imine / Allylboration / Homoally lamine / Polymer-supported regent / Oxazaborolidine / N-保護イミン
Research Abstract

Although the enantioselective synthesis of optically active amines by nucleophilic addition of organometallic reagents is a topic of current interest, the enantioselective addition of allylmetals to C=N double bond is quite underdeveloped in comparison to the effort on record in the area of asymmetric addition to carbonyl compounds. This research project aimed at design of asymmeric allylat ion reaction of imines, We have found that N-metallo imines such as N-silyl, N-aluminum, and N-borylimines were allylated with allylboron reagents to give the corresponding homoallylamines in good yield. Removal of N-substituents from the homoallylamines were quite easy. This approach is thus a novel efficient method for the synthesis of optically active primary homoallylamines. For example, N-silylimines were enantioselectively allylated with chirally modified allylboron reagent to give the homoallylamines in almost quantitative yield with high enantioselectivity (> 90% ee). To our knowledge, this … More is the first report of high level of asymmetric induction realized in the enantioselective addition of allylboron reagent to imines. Although N-silylimines derived from enolizable aldehydes resulted in the formation of complexed mixture as the product of allylat ion, N-alumino imines having alpha-proton could be allylated to give the homoallylamine. In the cases of the enantioselective allylation of N-alumino imines and N-boryl imines afforded the enantioenriched homoallylamines in good yield with high selectviity. It is noteworthy that high enantioselectivty (>80% ee) was attained even at room temperature when these imines were allylated.
Polymer-supported chiral reagents and catalysts are of interest in the field of asymmetric synthesis, since the chiral reagents can be recycled many times. In some cases, continuous flow system is possible by using polymer-suppored chiral catalyst. We have prepared polymer- supported chirally modified allylboron reagents. Asymmetric allylation of N-metallo imines described above with the polymer-supported reagents have been investigated. Polymer- supported N-sulfonylaminoalcohols derived from D-camphor or norephedrine were quite suitable chiral ligands for the allylation of imines. In spite of heterogeneous reaction using such polymers, sufficient reactivity and high enantioselelctivity was attained. This is also the first finding of the enantioselective allylation of imines using polymeric reagent. Less

Report

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

    (15 results)

All Other

All Publications (15 results)

  • [Publications] S.Itsuno: "Asymmetric reactions on polymers : diastereoselective allyl-ation of polymer-suported chiral imines" New Journal of Chemistry. 775-777 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Watanabe: "Enantioselective synthesis of optically active homoallylamines by allylboration of N-diisobutylaluminum imines" Journal of Organometallic Chemistry. (in press). (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S.Ituno, K.Watanabe, K.Ito, A.A.El-Shehawy and A.A.Sarhan: ""Enantioselective Synthesis of Homoallylamines by Nucleophilic Addition of Chirally Modified Allyboron Regents to Imines"" Angew.Chem.Int.Ed.Engl.36. 109-110 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.A.El-Shehawy, M.Y.Abdelaal, K.Watanabe, K.Ito and S.Itsuno: ""Enantioselective Allylation of N- (Trimethylsilyl) benzaldehyde Imine using Polymer-Supported chiral Allyboron Regents"" Tetrahedron : Asymmetry. 8. 1731-1734 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S.Itsuno, A.A.El-Shehawy and A.A.Sarhan: ""Enantiopure N-Sulfonylamino Alcohols and Their Copolymers as Chiral Auxiliaries for the Highly Enantioselective Allylboration of Aldehydes"" Reactive Polymers. 37. 283-287 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.A.El-Shehawy, M.A.Omara, K.Ito and S.Itsuno: ""Preparation of Both Diastereomers of Homoallylic Amines by Allylation of Methyl N-Benzylidene- (S) -valinate"" Synlett. 367-368 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Watanabe, S.Kuroda, A.Yokoi, K.Ito and S.Itsuno: ""Enantioselective Synthesis of Optically Active Homoallylamines by Allyboration of N-Diisobutylaluminum Imines"" J.Organomet.Chem.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S.Ituno: ""Progress in Applications of Chiral Polymers"" Kobunshi. 46. 90-94 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S.Itsuno: ""Enantioselective Reduction of Ketones"" Organic Reactions, (1998), 52, L.A.Paquette, et al. (Eds.). 395-576

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S.Itsuno: ""Hydroboration of C=O"" Comprehensive Asymmetric Catalysis" , E.N.Jacobsen, A.Pfalts and H.Yamamoto (Eds.), Springer. (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S.Itsuno: "Asymmetric reactions on polymers: diastereoselective allylation of polymer-supported chiral imines" New Journal of Chemistry. 775-777 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Watanabe: "Enantioselective synthesis of optically active homoallylamines by allylboration of N-diisobutylaluminum imines" Journal of Organometallic Chemistry. (in press). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] S.Itsuno他: "Enantioselective Allylation of N-(Trimethylsilyl)benzaldehyde Imine using Polymer-Supported Chiral Allylboron Reaqents" Tetrahedron:Asymmetry. 8. 1731-1734 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Itsuno他: "Enantiopure N-Sulfonylamino Alcohols and Their Copolymers as Chiral Auxiliaries for the Highly Enantioselective Allylboration" Reactive & Functional Polymers. (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Itsuno他: "Preparation of Both Diastereomers of Homoallylic Amines by Allylmetalation of Methyl N-Benzylidene-(S)-valinate" Synlett. (1998)

    • Related Report
      1997 Annual Research Report

URL: 

Published: 1997-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi