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Development of the effecient synthetic methods of some pharmeceuticals by using the generalized asymmetric epoxidation

Research Project

Project/Area Number 06558093
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section試験
Research Field Bioorganic chemistry
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

KATSUKI Tsutomu  Fac.Sci.Dept.Chem.KYUSHU UNIVERSITY,Professor, 理学部, 教授 (40037271)

Co-Investigator(Kenkyū-buntansha) OHARA Yoshio  Nissan Chem.Ind.Ltd.Res, Chairman, 企画研究部, 主査
IRIE Ryo  Fac.Sci.Dept.Chem.KYUSHU UNIVERSITY,Res.Associate, 理学部, 助手 (70243889)
Project Period (FY) 1994 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥6,500,000)
Fiscal Year 1996: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1995: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1994: ¥2,800,000 (Direct Cost: ¥2,800,000)
Keywordsasymmetric epoxidation / aziridination / (salen) manganese complex / benzylic hydroxylation / asymmetric oxidation / 不斉酸化 / エポキシド / 昆虫フェロモン / メタラオキセタン中間体
Research Abstract

We have studied on asymmetric epoxidation of simple olefins to provide a useful methodology for the synthesis of pharmaceuticals and found that well-designed (salen) manganese (III) complexes are efficient catalysts for epoxidation of conjugated olefins. To develop the more effective catalyst, we examined about the reaction mechanism of epoxidation using a (salen) manganese (III) catalyst this year and could propose a unique mechanism of asymmetric induction by the catalysts : the high asymmetric induction by salen catalyst is mainly attributable to asymmetric non-planar structure of the salen ligand. Based on this new knowledge, we could find that an achiral (salen) manganese (III) complex catalyzes epoxidation in the presence of an optically amine in a enantioselective manner. Although enantioselectivity of the reaction is not high enough for practical use at present, this new methodology using readily available and non-expensive achiral salen catalyst will lead to the development of more economical epoxidation.
We also developed asymmetric aziridination of styrane derivatives and asymmetric benzylic hydroxylation by the modification of the (salen) manganese (III) complex we had reported.
These new reactions are expected to be efficient tools for the synthesis of wide variety of pharmaceuticals.

Report

(4 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • Research Products

    (38 results)

All Other

All Publications (38 results)

  • [Publications] 濱田哲也: "Mechanism of One Oxygen Atom transfer from Oxo (salen) manganese (V) Complex to Olefins." Tetrahedron. 52・2. 515-530 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 福田勉: "Mn-Salen Catalyzed Asymmetric Oxidation of Enol Derivatives." Tetrahedron Letters. 37・25. 4389-4392 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 野口由紀子: "Mn-Salen Catalyzed Asymmetric Epoxidation of (±)-3-Alkylindene : Reagent-Dependent Stereoselectivity." Tetrahedron Letters. 37・26. 4533-4536 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 濱地清恵: "Asymmetric Benzylic Oxidation Using Mn-Salen Complex as a Catalyst." Tetrahedron Letters. 37・28. 4979-4982 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 小久保千穂: "Highly Enantioselective Catalytic Oxidation of Alkyl Aryl Sulfides with Mn-Salen Catalyst." Tetrahedron. 52・44. 13895-13900 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 端早田隆: "Enantioselective Epoxidation of 2,2-Dimethylchromenes Using Achiral Mn-Salen Complex as a Catalyst in the Presence of Chiral Amine." Synlett. ・11. 1079-1081 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 北島浩: "Enantioselective Addition of Diethylzinc to Aldehydes Using 1,1'-Bi-2-naph-thol-3,3'-dicarboxamide as a Chral Auxiliary" Chemistry Letters. ・5. 343-344 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 錦織寿: "Catalytic and Highly Enantioselective Aziridination of Styrene Derivatives" Tetrahedron Letters. 37・. 9245-9248 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 北島浩: "N,N,N',N'-Tetraalkyl-2,2'-dihydroxy-1,1'-binaphthyl-3,3'-dicarboxamides : Novel Chiral Auxiliaries for Asymmetric Simmons-Smith Cyclopropanation of Allylic" Bull.Chem.Soc.Jpn.70・1. 207-217 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 今西宏敏: "Stereochemistry in Asymmetric Epoxidation Using a (Salen) chromium (III) Complex as a Catalyst" Tetrahedron Letters. 38・. 251-254 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Hamada, T.Fukuda, H.Imanishi, and T.Katsuki: "Mechanism of One Oxygen Atom Transfer from Oxo (salen) manganese (V) Complex to Olefins." Tetrahedron. 52. 515-530 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Fukuda, and T.Katsuki: "Mn-Salen Catalyzed Asymmetric Oxidation of Enol Derivatives." Tetrahedron Lett.37. 4389-4392 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Noguchi, R.Irie, T.Fukuda, and T.Katsuki: "Mn-Salen Catalyzed Asymmetric Epoxidation of ((]SY.+-。[))-3-Alkylindene : Reagent-Dependent Stereoselectivity." Tetrahedron Lett.37. 4533-4536 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Hamachi, R.Irie, and T.Katsuki: "Asymmetric Benzylic Oxidation Using Mn-Salen Complex as a Catalyst." Tetrahedron Lett.37. 4979-4982 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Kokubo and T.Katsuki: "Highly Enantioselective Catalytic Oxidation of Alkyl Aryl Sulfides with Mn-Salen Catalyst." Tetrahedron. 52. 13895-13900 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Hashihayata, Y.Ito, and T.Katsuki: "Enantioselective Epoxidation of 2,2-Dimethylchromenes Using Achiral Mn-Salen Complex as a Catalyst in the Presence of Chiral Amine." Synlett.1079-1081 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Kitajima, K.Ito, and T.Katsuki: "Enantioselective Addition of Diethylzinc to Aldehydes Using 1,1'-Bi-2-naph-thol-3,3'-dicarboxamide as a Chral Auxiliary." Chem.Lett.343-344 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Nishikori and T.Katsuki: "Catalytic and Highly Enantioselective Aziridination of Stirene Derivaties" Tetrahedron Lett.37. 9245-9248 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Kitajima, K.Ito, Y.Aoki, and T.Katsuki: "N,N,N', N'-Tetraalkyl-2,2'-dihydroxy-1,1'-binaphthyl-3,3'-dicarboxamides : Novel Chiral Auxiliaries for Asymmetric Simmons-Smith Cyclopropanation of Allylic Alcohols and for Asymmetric Diethylzinc Addition to Aldehydes." Bull.Chem.Soc.Jpn.70. 207-217 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Imanishi and T.Katsuki: "Unusual Stereochemistry in Asymmetric Epoxidation Using a (Salen) chromium (III) Complex as a Catalyst" Tetrahedron Lett.38. 251-254 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 濱田 哲也: "Mechanism of One Oxygen Atom Transfer from Oxo(salen)manganese(V) Complex to Olefins." Tetrahedron. 52・2. 515-530 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 福田 勉: "Mn-Salen Catalyzed Asymmetric Oxidation of Enol Derivatives." Tetrahedron Letters. 37・25. 4389-4392 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 野口由紀子: "Mn-Salen Catalyzed Asymmetric Epoxidation of(±)-3-Alkylindene:Reagent-Dependent Stereoselectivity." Tetrahedron Letters. 37・26. 4533-4536 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 濱地 清恵: "Asymmetric Benzylic Oxidation Using Mn-Salen Complex as a Catalyst." Tetrahedron Letters. 37・28. 4979-4982 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 小久保 千穂: "Highly Enantioselective Catalytic Oxdation of Alkyl Aryl Sulfides with Mn-Salen Catalyst." Tetrahedron. 52・44. 13895-13900 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 端早田 隆: "Enantioselective Epoxidation of 2,2-Dimethylchromenes Using Achiral Mn-Salen Complex as a Catalyst in the Presence of Chiral Amine." Synlett. ・11. 1079-1081 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 北島 浩: "Enantioselective Addition of Diethylzinc to Aldehydes Using 1,1^1-Bi-2-naph-thol- 3,3^1-dicarboxamide as a Chral Auxiliary" Chemistry Letters. ・5. 343-344 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 錦織 寿: "Catalytic and Highly Enantioselective Aziridination of Styrene Derivatives" Tetrahedron Letters. 37・. 9245-9248 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 北島 浩: "N,N,N^1,N^1-Tetraalkyl-2,2^1-dihydrixy-1,1^1-binaphthyl-3,3^1-dicarboxamides:Novel Chiral Auxiliaries for Asymmetric Simmons-Smith Cyclopropanation of Allylic" Bull.Chem.Soc.Jpn.70・1. 207-217 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] 今西 宏敏: "Stereochemistry in Asymmetric Epoxidation Using a(Salen)choromium(III)Complex as a Catalyst" Tetrahedron Letters. 38・. 251-254 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] 福田 勉: "Mn-Salen Catalyzed Asymmeric Epoxidation of Conjugated Trisubstituted Olefins" Synlett. 197-198 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 三瓶 大輔: "Mn-Salen Catalyzed Asymmeric Epoxidation of 1,3-Cycloalkadienes and Dialkylsubstituted Z-olefins" Synlett. 827-828 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 濱田 哲也: "Insect Pheromone Synthesis Using Mn-Salen Catalyzed Asymmetric Epoxidation as a Key Step" Tetrahedron:Asymmetry. 6. 2441-2451 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 濱田 哲也: "Mechanism of One Oxygen Atom Transfer from Oxo(Salen) manganese(V) Complex to Olefins" Tetrahedron. 52. 515-530 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] 野田 健二: "Catalytic Asymmeric Oxidation of Sulfides Using(salen)manganese(III)Complex as a Catalyst" Tetrahedron. 50. 9609-9618 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 佐々木 英彦: "Rational Design of Mn-Salen Catalyst(2):Highly Enantioselective Epoxidation of Conjugated cis-Olefins" Tetrahedron. 50. 11827-11838 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 黒木 高志: "Synthesis of a New Chiral Auxiliary,(1R,2R,3R,6R)-3,6-Dimethylcyclohexane-1,2-diamine" Chemistry Letters. (印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] 黒木 高志: "Synthesis of Mn-Salen Catalyst Bearing (1R,2R,3R,6R)-3,6-Dimethylcyclohexane-1,2-diamine as an Ethylene diamine Part and Its Application to Asymmetric Epoxidation" Chemistry Letters. (印刷中). (1995)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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