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LATTICE-CONTROLLED SOLID STATE-SPECIFIC AND ENANTIOSELECTIVE REACTIONS

Research Project

Project/Area Number 04640516
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionNIIGATA COLLEGE OF PHARMACY

Principal Investigator

OHGO Yoshiaki  NIIGATA COLLEGE OF PHARMACY,DEPARTMENT : PHARMACY,TITLE OF POSITION : PROFESSOR, 薬学部, 教授 (10016115)

Co-Investigator(Kenkyū-buntansha) MIYOSHI Norikazu  NIIGATA COLLEGE OF PHARMACY,DEPARTMENT : PHARMACY,TITLE OF POSITION : ASSISTANT, 薬学部, 助手 (40219829)
ARAI Yoshifusa  NIIGATA COLLEGE OF PHARMACY,DEPARTMENT : PHARMACY,TITLE OF POSITION : ASSISTANT, 薬学部, 助手 (40202725)
TAKEUCHI Seiji  NIIGATA COLLEGE OF PHARMACY,DEPARTMENT : PHARMACY,TITLE OF POSITION : ASS.PROFES, 薬学部, 助教 (00131011)
Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1993: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1992: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsSolid-State Reaction / Asymmetric Reaction / Isomerization / Photoreaction / Chiral Lattice / Organocobalt Complex / Optically Active / Racemization
Research Abstract

Previously, we found solia state-specific phenomenon in the photoracemization of optically active alkyl cobaloxime complexes. We also found solid state-specific and unidirectional (betha to alpha) photoisomerization of 2-substituted ethyl cobaloxime complexes.
This study was carried out to clarify the mechanism for the above mentioned solid state-specific phenomenon and to find chiral lattice-controlled asymmetric (betha to alpha) photoisomerization, and the following results [ (1)- (3)] were obtained.
(1) The solid state-specific phenomenon in the photoracemization of optically active alkyl cobalocime complexes was attributed (ascribed) to an unsymmetrical restriction of the reactive group by an intermolecular interaction such as hydrogen bonding.
(2) Solid-state asymmetric photoisomerization occurred to afford optically active 1-substituted ethyl cobaloxime complexes with moderate to high enantioselectivities (up to 88%ee) upon visible light-irradiation on 2-cyanoethyl, 2-methoxycarbonylethyl, and N-substituted 2-carbamoylethyl cobaloximes coordinated with chiral axial ligand which has no asymmetric effect on the reactive group at the trans position in the same molecule but serves as the chiral handle for forming the chiral lattice.
(3) The X-ray crystallographic analyzes of a series of 2-cyanoethyl and 2-methoxycarbonylethyl cobaloximes revealed that the 2-substituted ethyl group in a complex bringing about high enantioselectivity is apt to take a conformation parallel to the inplane ligand and is also forced to take a chiral conformation by chiral lattice, while the reactive group in a complex bringing about low enantioselectivity take a conformation perpendicular to the inplane ligand.

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] Y.Sakaki: "Multi-stage Crystalline State Racemization of a Bulky Chiral Group," Mol.Cryst.Liq.Cryst.,. 219. 149-152 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Y.Takenaka: "Temperature Dependence of Reaction Rate in Crystalline State Racemization" Mol.Cryst.Liq.Cryst.,. 219. 153-156 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Y.Takenaka: "Crystalline-State Racemization of a Chiral Cyanoethyl Group Connected by a Hydrogen Bond" Acta Cryst.,. B49. 272-277 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Y.Sakaki: "Crystalline-State Racemization of Cobaloxime Complexes.17.Requirements for Racemization of the Buiky Dimethyoxycarbonylethyl Group" Acta Cryst.,. B49. 1010-1014 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Y.Ohgo: "Chiral Lattice-Controlled Asymmetric Photoisomerization of (2-Cyanoethyl)cobaloximes in the Solid State" Chem.Lett.,. 1994. 715-718 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 大胡 恵明: "光学活性有機コバルト錯体の合成とその液相および固相・結晶相反応" 有機合成化学協会誌、. 51. 592-607 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] ed by Y.Ohashi: "“Reactivity in Molecular Crystals"" Kodansha,Tokyo, 348 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yoshii Sakai et al.: "Multi-Stage Crystalline State Racemization of a Bulkyl Chiral Group" Mol.Cryst.Lig.Cryst.219. 149-152 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yasuyuki Takenaka et al.: "Temperature Dependence of Reaction Rate in Crystalline State Racemization" Mol.Cryst.Lig.Cryst.219. 153-156 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yasuyuki Takenaka et al.: "Crystalline-State Racemization of a Chiral Cyanoethyl Group Connected by a Hydrogen Bond" Acta Cryst.B49. 272-277 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yoshii Sakai et al.: "Crystalline-State Reaction of Cobaloxime Complexes. 17. Requirements for Racemization of the Bulky Dimethoxycarbonylethyl Group" Acta Cryst.B49. 1010-1014 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yoshiaki Ohgo et al.: "Chiral Lattice-Controlled Asymmetric Photoisomerization of (2-Cyanoethyl) cobaloximes in the Solid State" Chem.Lett.1994. 715-718 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Y.Ohgo: "Syntheses and Reactions of Chiral Organocobalt Complexes in Solution, and in the Solid and Crystalline State (review)" J.Synth.Org.Chem.Jap.51. 592-607 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yuji Ohashi, Ed.: Reactivity in Molecular Crystals. Kodansha, 348 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Y.Sakai: "Crystalline-State Reaction of Cobaloxime Complexes.17.Require-ments for racemization of Bulky Dimethoxycarbonylethyl group" Acta Crystallogr.B49. 1010-1014 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Y.Ohgo: "Chiral Lattice-Controlled Asymmetric Photoisomerization of(2-Cyanoethyl)cobaloximes in the Solid State" Chem.Lett.1994. 715-718 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yuji Ohashi(Ed.): "Reactivity in Molecular Crystals" Kodansha/VCH, 348 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Y.Sakai,Y.Ohashi,Y.Arai,Y.Ohgo: "Multi-stage Crystalline State Racemization of A Bulkyl Chiral Group" Mol.Cryst.Liq.Cryst.,. 219. 149-152 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Takanaka,Y.Kojima,Y.Ohashi,Y.Ohgo: "Temperature Dependence of Reaction Rate in Crystalline State Racemization" Mol.Cryst.Liq.Cryst.,. 219. 153-156 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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