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Development of catalytic asymmetric reactions based on a molecular assembly

Research Project

Project/Area Number 14572001
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

TAKEMOTO Yoshiji  Kyoto University, Graduate School of Pharmaceutical Sciences, Professor, 薬学研究科, 教授 (20227060)

Co-Investigator(Kenkyū-buntansha) YANADA Reiko  Kyoto University, Graduate School of Pharmaceutical Science, Research assistant, 薬学研究科, 助手 (80239821)
Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2003: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2002: ¥2,100,000 (Direct Cost: ¥2,100,000)
Keywordsquaternary ammonium salt / thiourea / micelle / hydrogen bonding / molecular assembly / iridium / allylic alkylation / Michael addition / 多機能性触媒 / ニトロオレフィン / アミノ酸類 / パラジウム / 不斉配位子
Research Abstract

1.With an aim of proper alignment of the prepared ammonium catalysts in a micelle, we designed and synthesized four ammonium catalysts, which possess alkyl and poly-ether side-chains into the cinchonidine. Although we have developed a convenient method for the introduction of alkyl and poly-ether groups into the cinchonidine-derived quatemary ammonium salts, the asymmetric alkylation of imino glycinate using these catalysts only gave rise to the corresponding products with lower enantioselectivity than that of the original catalyst.
2.We have developed the first enantioselective Ir-catalyzed allylic substitutions of diphenylimino glycinate by using chiral bidentate ligand (up to 98% ee), and also succeeded in the diastereoselective asymmetric synthesis of both diastereomers by simply switching the base employed such as KOH (method A) and LiHMDS (method B).
3.Since we succeeded in the enantioselective synthesis of the branch products, we next investigated the asymmetric synthesis of quaternary amino acids using the Ir-catalyzed allylic alkylation of various alaninates. The adoption of method B to phosphate and alaninate gave chiral quaternary amino acids with acceptable yield and stereoselectivity.
4.We found that thiourea dramatically enhanced the nucleophilic addition of TMSCN and ketene silyl acetals to nitrones and aldehydes. Furthermore, thiourea bearing a tertiary amino group worked well as a bifunctional organocatalyst, and promoted the Michael reaction of malonates to various nitroolefins with high enantioselectivities. The reaction was also successful without solvent.

Report

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

    (36 results)

All Other

All Publications (36 results)

  • [Publications] H.Ohno et al.: "Synthesis of allenes from allylic alcohol derivatives bearing a bromine atom using a palladium(0)/diethylzinc system"J.Org.Chem.. 67・4. 1359-1367 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Nakoji et al.: "Pd-Catalyzed Asymmetric Allylic Alkylation of Glycine Iminoester Using a Chiral Phase-Transfer Catalyst"J.Org.Chem.. 67・21. 7418-7423 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Matsushita et al.: "Synthetic study on CP-263,114 (phomoidride B) by SET-mediated fragmentation"Chem.Commun.. 8. 814-815 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] R.Yanada et al.: "OsO_4-catalyzed dihydroxylation of olefins in ionic liquid [emim]BF_4 : a recoverable and reusable osmium"Tetrahedron Lett.. 43・38. 6849-6852 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Anzai et al.: "Asymmetric synthesis of β2,3-amino acids by InI-Pd(0)-promoted metalation and addition of chiral 2-vinylaziridines"Tetrahedron. 58・26. 5231-5239 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] R.Yanada et al.: "Indium-mediated atom-transfer cyclizations and reductive cyclizations"Tetrahedron Lett.. 43・26. 4585-4588 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Kanayama et al.: "Synthesis of β-Substituted α-Amino Acids Using Iridium-Catalyzed Asymmetiic Allylic Substitution"J.Org.Chem.. 68・16. 6197-6201 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Miyabe et al.: "O-Allylic Substitution of Hydroxylamine Derivatives Having an N-Electron-Withdrawing Substituent"Synlett. 4. 567-569 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Okino et al.: "Thiourea-catalyzed nucleophilic addition of TMSCN and ketene silyl acetals to nitrones and aldehydes"Tetrahedron Lett.. 44・8. 2817-2821 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Okino et al.: "Enantioselective Michael Reaction of Malonates to Nitroolefins Catalyzed by Bifunctional Organocatalysts"J.Am.Chem.Soc.. 125・42. 12672-12673 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Kanayama et al.: "Enantio- and Diastereoselective Ir-Catalyzed Allylic Substitutions for Asymmetric Synthesis of Amino Acid Derivatives"Angew.Chem.Int.Ed.. 42・18. 2054-2056 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] A.Fukuda et al.: "Synthetic Studies on Macrolactin A by Using a (Diene)Fe(CO)_3 Complex"Tetrahedron. 59・47. 9305-9313 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Ohno et al.: "Synthesis of allenes from allylic alcohol derivatives bearing a bromine atom using a palladium(O)/diethylzinc system"J.Org.Chem.. 67. 1359-1367 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Nakoji et al.: "Pd-Catalyzed Asymmetric Allylic Alkylation of Glycine Iminoester Using a Chiral Phase-Transfer Catalyst"J.Org.Chem.. 67. 7418-7423 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Matsushita et al.: "Synthetic study on CP-263,114 (phomoidride B) by SET-mediated fragmentation"Chem.Commun.. 814-815 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] R.Yanada et al.: "OsO_4-catalyzed dihydroxylation of olefins in ionic liquid [emim]BF_4: a recoverable and reusable osmium"Tetrahedron Lett.. 43. 6849-6852 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Anzai et al.: "Asymmetric synthesis of β^<2,3> -amino acids by InI-Pd(O)-promoted metalation and, addition of chiral 2-vinylaziridines"Tetrahedron. 58. 5231-5239 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] R.Yanada et al.: "Indium-mediated atom-transfer cyclizations and reductive cyclizations"Tetrahedron Lett.. 43. 4585-4588 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Kanayama et al.: "Synthesis of β-Substituted α-Amino Acids Using Iridium-Catalyzed Asymmetric Allylic Substitution"J.Org.Chem.. 68. 6197-6201 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Miyabe et al.: "O-Allylic Substitution of Hydroxylamine Derivatives Having an N-Electron-Withdrawing Substituent"Synlett. 567-569 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Okino et al.: "Thiourea-catalyzed nucleophilic addition of TMSCN and ketene silyl acetals to nitrones and aldehydes"Tetrahedron Lett.. 44. 2817-2821 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Okino, Y.Hoashi, Y.Takemoto: "Enantioselective Michael Reaction of Malonates to Nitroolefins Catalyzed by Bifunctional Organocatalysts"J.Am.Chem.Soc.. 125. 12672-12673 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Kanayama et al.: "Enantio-and Diastereoselective Ir-Catalyzed Allylic Substitutions for Asymmetric Synthesis of Amino Acid Derivatives"Angew.Chem.Int.Ed.. 42. 2054-2056 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] A.Fukuda et al.: "Synthetic Studies on Macrolactin A by Using a (Diene)Fe(CO)_3 Complex"Tetrahedron. 59. 9305-9313 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Kanayama et al.: "Synthesis of b-Substituted a-Amino Acids Using Iridium-Catalyzed Asymmetric Allylic Substitution"J.Org.Chem.. 68・16. 6197-6201 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Miyabe et al.: "O-Allylic Substitution of Hydroxylamine Derivatives Having an N-Electron-Withdrawing Substituent"Synlett. 4. 567-569 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Okino et al.: "Thiourea-catalyzed nucleophilic addition of TMSCN and ketene silyl acetals to nitrones and aldehydes"Tetrahedron Lett.. 44・8. 2817-2821 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Okino et al.: "Enantioselective Michael Reaction of Malonates to Nitroolefins Catalyzed by Bifunctional Organocatalysts"J.Am.Chem.Soc.. 125・42. 12672-12673 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Kanayama et al.: "Enantio- and Diastereoselective Ir-Catalyzed Allylic Substitutions for Asymmetric Synthesis of Amino Acid Derivatives"Angew.Chem.Int.Ed.. 42・18. 2054-2056 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] A.Fukuda et al.: "Synthetic Studies on Macrolactin A by Using a (Diene)Fe(CO)_3 Complex"Tetrahedron. 59・47. 9305-9313 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Ohno et al.: "Synthesis of allenes from allylic alcohol derivatives bearing a bromine atom using a palladium(0)/diethylzinc system"J. Org. Chem.. 67・4. 1359-1367 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Nakoji et al.: "Pd-Catalyzed Asymmetric Allylic Alkylation of Glycine Iminoester Using a Chiral Phase-Transfer Catalyst"J. Org. Chem.. 67・21. 7418-7423 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Matsushita et al.: "Synthetic study on CP-263,114 (phomoidride B) by SET-mediated fragmentation"Chem. Commun.. 8. 814-815 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] R.Yanada et al.: "OsO_4-catalyzed dihydroxylation of olefins in ionic liquid [emim]BF_4 : a recoverable and reusable osmium"Tetrahedron Lett.. 43・38. 6849-6852 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Anzai et al.: "Asymmetric synthesis of β^<2,3>-amino acids by Inl-Pd(0)-promoted metalation and addition of chiral 2-vinylaziridines"Tetrahedron. 58・26. 5231-5239 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] R.Yanada et al.: "Indium-mediated atom-transfer cyclizations and reductive cyclizations"Tetrahedron Lett.. 43・26. 4585-4588 (2002)

    • Related Report
      2002 Annual Research Report

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

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