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Development of new chiral hetero-hybrid ligands and their use in catalytic asymmetric synthesis

Research Project

Project/Area Number 11672111
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) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2000: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1999: ¥1,800,000 (Direct Cost: ¥1,800,000)
Keywordschiral ligand / phosphine ligand / palladium catalyst / chiral catalyst / asymmetric allylation / enantioselectivity / ketene silyl acetal / asymmetric hydrosilylation / キラル素子 / カルボアニオン / キラリティ / イミノ-ホスフィン配位子 / ジホスフィン配位子 / ロジウム触媒 / ヒドロシリル化
Research Abstract

Several new types of chiral ligands such as phosphine-amidine-type and phosphine-imine-type ligands (P,N-hetero-hybrid ligands) and bis (amide-phosphine)-type ligands (P,P-symmetric ligands) were prepared in one step from versatile chiral components, β-(diphenylphosphino) alkylamines, which were synthesized in good overall yields from β-aminoalcohols obtained by reduction of α-amino acids. Both an amidine-type ligand VALAP and an imine-type ligand bearing an electron-donating group (p-Me_2N-) at the N-benzylidene group were found to be efficient ligands (>90% ee) in palladium-catalyzed asymmetric allylic alkylation of an acyclic allyl ester, 1,3-diphenyl-2-propenyl ester, with dimethyl malonate in the presence of BSA and AcOLi. Electron-donating groups at the p-position of the imine-type ligands were revealed to bring considerarble improvements of the enantioselectivity and the catalytic activity. High enantioselectivity was also obtained in the allylic alkylation by using ketene silyl acetals as nucleophiles in place of the corresponding monoester carbanions which are harder and less efficient nucleophiles than the malonate carbanion. On the other hand, a bis (amide-phosphine)-type ligand bearing a phthaloyl spacer was found to be a highly enantioselective ligand (>99% ee) for Pd-catalyzed allylic alkylation of a cyclic allyl ester, 2-cyclohexenyl ester. With analogous bis (amide-phosphine)-type ligands bearing different alkane spacers, an unusual reversal of chirality was observed in the allylic alkylation of 1,3-diphenyl-2-propenyl ester. Asymmetric rhodium-catalyzed hydrosilylation of ketones was also examined with the P,P-ligands. A useful concept of Pr/Mr-chirality was proposed for classification of all chiral bidentate ligands and a good correlation was observed between the Pr/Mr-chirality of the ligands and the absolute configuration of the allylation products.

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report

Research Products

(15 results)

All Other

All Publications (15 results)

  • [Publications] Akihito Saitoh: "A remarkable improvement of catalytic performance by electronic substituent effects of chiral P-N hybrid ligands in palladium-mediated asymmetric allylations."Synlett. 483-485 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh: "A new C2-symmetric chiral diphosphine ligand : palladium-catalyzed enantioselective allylic alkylation of cycloalkenyl substrate."Tetrahedron : Asymmetry. 10. 1025-1028 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh: "A new class of C2-symmetric diphosphine ligands derived from valine : remarkably diverse behavior in catalytic asymmetric transformations."Tetrahedron : Asymmetry. 10. 4501-4511 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh: "Versatile chiral bidentate ligands derived from α-amino acids : Synthetic applications and mechanistic considerations in palladium-mediated asymmetric allylic substitutions."J.Org.Chem.. 65. 4227-4240 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh: "Induction of reversal chirality by C2-symmetric diamide linked-diphosphine ligands in catalytic asymmetric allylations."Tetrahedron : Asymmetry. 11. 4049-4053 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh, Mie Misawa, and Toshiaki Morimoto^*: "A remarkable improvement of catalytic performance by electronic substituent effects of chiral P-N hybrid ligands in palladium-mediated asymmetric allylations."Synlett. 483-485 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh, Mie Misawa, and Toshiaki Morimoto^*: "A new C_2-symmetric chiral diphosphine ligand : Palladium-catalyzed enantioselective allylic alkylation of cycloalkenyl substrate."Tetrahedron : Asymmetry. 10. 1025-1028 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh, Takashi Uda, and Toshiaki Morimoto^*: "A new class of C2-symmetric diphosphine ligands derived from valine : Remarkably diverse behavior in catalytic asymmetric transformations."Tetrahedron : Asymmetry. 10. 4501-4511 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh, Kazuo Achiwa, Kiyoshi Tanaka, and Toshiaki Morimoto^*: "Versatile chiral bidentate ligands derived from α-amino acids : Synthetic applications and mechanistic considerations in palladium-mediated asymmetric allylic substitutions.."J.Org.Chem.. 65. 4227-4240 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh, Takashi Uda, and Toshiaki Morimoto^*: "Induction of reversal chirality by C2-symmetric diamide linked-diphosphine ligands in catalytic asymmetric allylations"Tetrahedron : Asymmetry. 11. 4049-4053 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihito Saitoh: "Versatile chiral bidentate ligands derived from α-amino acids : Synthetic applications and mechanistic considerations in palladium-mediated asymmetric allylic substitutions."J.Org.Chem.. 65・14. 4227-4240 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Akihito Saitoh: "Induction of reversal chirality by C2-symmetric diamide linked-diphosphine ligands in catalytic asymmetric allylations."Tetrahedron : Asymmetry. 11・51. 4049-4053 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Akihito Saitoh: "A Remarkable Improvement of Catalytic Performance by Electronic Substituent Effects of Chiral P-N Hybrid Ligands in Palladium-Mediated Asymmetric Allylations"Synlett. 483-485 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Akihito Saitoh: "A New C_2-Symmetric Chiral Diphosphine Ligand:Palladium-Catalyzed Enantioselective Allylic Alkylation of Cycloalkenyl Substrate"Tetrahedron Asymmetry. 10. 1025-1028 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Akihito Saitoh: "A New Class of C_2-Symmetric Diphosphine Ligands Derived from Valine:Remarkably Diverse Behavior in Catalytic Asymmetric Transformations"Tetrahedron Asymmetry. 10. 4501-4511 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-03-31   Modified: 2016-04-21  

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