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Selfassembly of Molecules in Crystal and Its Application to Selective Synthesis

Research Project

Project/Area Number 03303002
Research Category

Grant-in-Aid for Co-operative Research (A)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionEhime University

Principal Investigator

TODA Fumio  Faculty of Engineering, Ehime University, Professor, 工学部, 教授 (50036232)

Co-Investigator(Kenkyū-buntansha) KOBAYASHI Keiji  Faculty of General Education, The University of Tokyo, Professor, 教養学部, 教授 (50012456)
MIYATA Kanji  Faculty of Engineering, Gifu University, Associate Professor, 工学部, 助教授 (90029322)
SAKAINO Yoshiko  Faculty of Education, Gunma University, Professor, 教育学部, 教授 (70008142)
FUJIWARA Takaji  Faculty of Science, Shimane University, Professor, 理学部, 教授 (10028847)
樋口 泰一  大阪市立大学, 理学部, 教授 (40046868)
Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥9,700,000 (Direct Cost: ¥9,700,000)
Fiscal Year 1992: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 1991: ¥7,000,000 (Direct Cost: ¥7,000,000)
Keywordsinclusion crystal / chiral recognition / optical resolution / ammonium salt / bis-beta-naphthol / bisphenanthrol / hydrogen bond / chiral shift reagent / アンモニウム塩ホスト / ビス-β-ナフトール / 包接体結晶 / 固相反応 / ホストーゲスト錯体 / 不斉合成 / 不斉発現 / クリスタルエンジニアリング / 光学活性ホスト
Research Abstract

Application of the chiral recognition in a host-quest inclusion crystal to optical resolution of the guest compound is successful. The optically active host compounds which were derived from tartaric acid were found to be effective for optical resolution of various guest compounds. Chiral recognition by the optically active diacetylenic alcohol host compound depends delicatelly on its chemical structure. For example, although the optically active diacetylenic alcohol host is not effective for the resolution of an important starting material of prostaglandin synthesis, hydroxycyclopentenone, the diacetylenic alcohol host compound which has p-disubstituted phenyl group between the two acetylenic groups works very well for the resolution.
However, alkaloid such as brucine was found to be effective for the resolution of benzhydrol derivatives. Interestingly, the benzhydrol which has a substituent on meta- or para-position of one phenyl group,was resolved efficiently by complexation with bru … More cine. However, the benzhydrol which has an ortho-substituent was not. The structure dependence in the chiral recognition seems to be relating to so called the ortho-effect in organic chemistry in solution.
The most interesting finding is the chiral recognition with cinchonidium chloride host. N-Benzoylcinchonidium chloride formed a 1:1 inclusion crystal with 2,2'-dihydroxy-1,1'-binaphthyl. By using the complexation, the latter was resolved very effectively. X-ray crystal structure analysis of the inclusion crystal showed that the hydroxyl group of the binaphthol forms a hydrogen bond network with the chloride anion. Interestingly, the N-benzylcinchonidium chloride was not effective for 10,10'-dihydroxy-9,9'-biphenanthryl which was, however, resolved easily by complexation with N-butylcinchonidium chloride.
Some fruitful results were obtained in the study of enantioselective reaction in inclusion crystal. For example, photoirradiation of cyclohexenone and coumarin in their inclusion crystal with an optically active host compound gave optically active dimer. Photoirradiation of an inclusion crystal of acrylanilide with an optically active host gave optically active dihydroquinolinone derivative. The enantioselectivity of these photoreactions in inclusion crystals is almost perfect and optically almost pure enantiomers were obtained. Enantioselective Michael reaction in inclusion crystal was also successful.
It was also disclosed that most chiral hosts work as chiral shift reagents. Less

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] Koichi Tanaka: "Selective Photodimerisations of Coumarin in Crystalline Inclusion Compounds" J.Chem.Soc.Perkin Trans.1. 307-307 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Tanaka: "Efficient Optical Resolution of Some Key Compounds of Prostaglandin Synthesis" J.Chem.Soc.Perkin Trans.1. 517-520 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Fumio Toda: "Photocyclisation of Phenylglyoxylamides as Inclusion Complexes with an Optically Active Host Derived from Tartaric Acid" J.Chem.Soc.Perkin Trans.1. 1461-1462 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Tanaka: "Control of the Stereochemistry in the Photocyclisation of Acrylanilides to 3,4-Dihydroquinolin-2(1H)-ones" J.Chem.Soc.,Chem.Commun.1053-1054 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Mino Caira: "Complexation with Diol Host Compounds.Part 9.Structures and Thermal Analyses of Inclusion Compounds of trans-9,10-dihydroxy-9,10-dihydroanthracene with Acetonitrile" Thermochimica Acta. 205. 265-271 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Fumio Toda: "Inclusion Complexation of Cholestanol,Cholesterol,Sitosterol,Stigmasterol,and Ergosterol with Various Guests" Bull.Chem.Soc.Jpn.66. 320-323 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Fumio Toda: "Molecular Recognition in the Solid State" JAI Press Inc.(London), 195 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Fumio Toda: "Selective Reactions in the Solid State" Kodansha(Tokyo), 463 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K. Tanaka: "Selective Photodimerisations of Coumarin in Crystalline Inclusion Compounds" J. Chem. Soc. Perkin Trans. 1. 307-307 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Tanaka: "Efficient Optical Resolution of Some Key Compounds of Prostaglandin Synthesis" J. Chem. Soc. Perkin Trans. 1. 517-520 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Fumio Toda: "Photocyclisation of Phenylglyoxylamides as Inclusion Complexes with an Optically Active Host Derived from Tartaric Acid" J. Chem. Soc. Perkin Trans. 1. 1461-1462 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Tanaka: "Control of the Stereochemistry in the Photocyclisation of Acrylanilides to 3,4-Dihydroquinolin-2-2(1H)-ones" J. Chem. Soc., Chem. Commun.1053-1054 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Mino Caira: "Complexation with Diol Host Compounds. Part 9. Structures and Thermal Analyses of Inclusion Compounds of trans-9,10-Dihydroxy-9,10-dihydro anthracene with Acetonitrile" Thermochimica Acta. 205. 265-271 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Fumio Toda: "Inclusion Complexation of Cholestanol, Cholesterol, Sitosterol, Stigmasterol, and Ergaosterol with Various Guests" Bull. Chem. Soc. Jpn.66. 320-323 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Fumio Toda: "Molecular Recognition in the Solid State" JAI Press Inc. (London). 141-191 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Fumio Toda: "Selective Reactions in the Solid State" Kodansha (Tokyo). 423-475 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Koichi Tanaka: "Selective Photodimerisations of Coumarin in Crystalline Inclusion Compounds" J. Chem. Soc. Perkin Trans. 1. 307-307 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Koichi Tanaka: "Efficient Optical Resolution of Some Key Compounds of Prostaglandin Sy nthesis" J. Chem. Soc. Perkin Trans. 1. 517-520 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Fumio Toda: "Photocyclisation of Phenylglyoxylamides as Inclusion Complexes with an Optically Active Host Derived from Tartaric Acid" J. Chem. Soc. Perkin Trans. 1. 1461-1462 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Koichi Tanaka: "Control of the Stereochemistry in the Photocyclisation of Acrylanilides to 3,4-Dihydroquinolin-2(1H)-ones" J. Chem. Soc.,Chem. Commun.1053-1054 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Mino Caira: "Complexation with Diol Host Compounds. Prart 9. Structures and Thermal Analyses of Inclusion Compounds of trans-9,10-dihvdroxy-9,10-dihydroanthracene with Acetonitrile" Thermochimica Acta. 205. 265-271 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Fumio Toda: "Inclusion Complexation of Cholestanol, Cholesterol, Sitosterol, Stigmasterol,and Ergosterol with Various Guests" Bull. Chem. Soc. Jpn.66. 320-323 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Fumio Toda: "Molecular Recognition in the Solid State" JAI Press Inc.(London), 195 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Fumio Toda: "Selective Reactions in the Solid State" Kodansha(Tokyo), 463 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] F.Toda,: "Optical Resolution of Amino Acid and Hydroxycarboxylic Acid Esters by Complexation with Optically Active Host Compounds: a Crystallographic Result" J.Chem.Soc.Perkin Trans.2. 1971-1975 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] F.Toda,: "Optical Resolution of Bicyclo〔2.2.1〕heptanone, Bicyclo〔2.2.2〕octanone, and Bicyclo〔3.2.1〕octanone Derivatives by Inclusion Complexation with Optically Active Host" J.Org.Chem.56. 7332-7335 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] F.Toda: "Efficient Resolution of Secondary Alcohols, Cyanohydrins, and Glycerol Acetals by Complexation with the Host Derived from Tartaric Acid" Tetrahedron Assym.2. 983-986 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] F.Toda: "A Novel preparation Method for Unsymmetrical Ethers by the Reaction of Cocrystal of Two Similarly Substituted Secondary Alcohols with Tolueneーpーsulphonic Acid in the Solid State" J.Chem.Soc.,Chem.Commun.1212-1213 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] S.A.Bourne: "Complexation with Diol Host Compounds.Part 7. Structure and Thermal Analysis of 1,2,2ーTetraphenylethaneー1,2ーdiol with Lutidine Guests" J.Chem.Soc.Perkin Trans.2. 1335-1341 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] D.R.Bond: "Complexation with Diol Host Compounds. Part 6. Structure and Dynamics of Enclathration by 1,1,6,6ーTetrapheylhexaー2,4ーdiyneー1,6ーdiol" J.Solid State Chem.92. 68-79 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] F.Toda: "Inclusion Compounds Vo1.4" Oxford University Press, 511 (1991)

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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