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Development and Application of New Chiral Ligand Systems Effective for Catalytic Asymmetric Carbon-Carbon Bond Formation

Research Project

Project/Area Number 13672225
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionUniversity of Shizuoka

Principal Investigator

MORIMOTO Toshiaki  University of Shizuoka, School of Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (60046307)

Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2003: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2002: ¥900,000 (Direct Cost: ¥900,000)
Keywordschiral ligand / chiral catalyst / copper catalyst / phosphine ligand / conjugate addition / enone / diethylzinc / enantioselectivity / スルホンアミド配位子 / 共役付加
Research Abstract

New chiral P,N type ligands were designed and prepared starting from L-valinol and (R)-binaphthol for catalytic asymmetric conjugate addition of dialkylzinc to enones. By condensation of a chiral component, (S)-1-(diphenylphosphino)-3-methyl-2-butanamine, with pyridine-2-carboxylic acids and pyridine-2-carboxaldehydes, new amide-type and imine-type P,N ligands bearing pyridyl groups were obtained. For evaluation of the ligands, asymmetric conjugate addition of diethylzinc to 2-cyclohexen-1-one was carried out using copper triflate (1 mol%) as the catalyst. The pyridylmethylene derivatives (imine-type ligands) were found to be very efficient ligands having high enantioselectivity up to 95% ee, though the amide-type ligands showed lower enantioselectivity (below 66% ee). On the other hand, the enantioselectivity of the conjugate addition to an acyclic enone, chalcone, was lower and only a moderate selectivity (up to 71% ee) was obtained even by using the imine-type ligands. The enantioselectivity of the amide-type ligand was improved by alkylation of the NH group, and the smallest N-Me derivative showed the highest selectiveity (81% ee (cyclohexenone), 75% ee (chalcone)). Several N-sulfonyl derivatives of the chiral component were prepared and the selectivity of an N-(1R)-10-camphorsulfonyl derivative (73% ee) was better than that of the others in the reaction of 2-cyclohexen-1-one. An axially chiral 1,1'-binaphthyl ligand bearing both 2-tosylamino and 2'-diphenylphosphino groups was synthesized through a new convenient route using (R)-2-cyano-2'-phosphinyl-1,1'-binaphthyl as a synthetic intermediate. The new ligand was found to be highly efficient in the copper-catalyzed conjugate addition of diethylzinc to benzylideneacetones, showing high selectivity of 84-99% ee.

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (2 results)

All Other

All Publications (2 results)

  • [Publications] Toshiaki Morimoto: "A new chiral 2-sulfonylamino-2'-phosphino-1,1'-binaphthyl ligand for highly enantioselective copper-catalyzed conjugate addition of diethylzinc to beozylideneacetones"Tetrahedron Letters. 45(in press). (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Toshiaki Morimoto: "A new chiral 2-sulfornylamino-2'-phosphino-1,1'-binaphthyl ligand for highly enantioselective copper-catalyzed conjugate addition of diethylzinc to benzylideneacetones."Tetrahedron Letters. 45(in press). (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary

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Published: 2002-04-01   Modified: 2016-04-21  

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