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Elucidation of Biradical Character in pi-Conjugated Hydrocarbons Caused by Annelation with Strained Bicycloalkene Frameworks

Research Project

Project/Area Number 14340196
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKYOTO UNIVUERSITY

Principal Investigator

KOMATSHU Koichi  Kyoto University, Institute for Chemical Research, Professor, 化学研究所, 教授 (70026243)

Co-Investigator(Kenkyū-buntansha) NISHINAGA Tohru  Kyoto University, Institute for Chemical Research, Assistant Professor, 化学研究所, 助手 (30281108)
Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 2003: ¥4,800,000 (Direct Cost: ¥4,800,000)
Fiscal Year 2002: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywordsaromaticity / antiaromaticity / sigma-pi interaction / bicyclic hydrocarbon / cyclooctatetraene / radical cation / X-ray crystallography / oligothiophene / 分子軌道計算 / NICS / クロスカップリング / 電気化学 / 一電子酸化反応 / 高歪みナフタレン / 大環状ジケトン / ジチイン / 渡環相互作用
Research Abstract

(1)The most essential aromatic hydrocarbon, benzene (1), and cyclic polyene, cyclooctatetraene (COT, 2), annelated with a highly strained bicyclic system, bicyclo[2.1.1]hexene (BCH), were synthesized. Their aromaticity and antiaromaticity were examined by the use of theoretical calculations and spectral and electrochemical measurements.
(2) One-electron oxidation of benzene 1 with SbCl_5 was found to cause rearrangement of 1 to a novel naphthalene derivative 3 annelated with the BCH units at 1,2- and 3,4-positions. The X-ray structural analysis of 3 demonstrated that the BCH-annelated 6-membered ring is more aromatic than the other ring owing to bond-length equalization. It can be oxidized to a stable radical cation because of the considerably raised HOMO energy levels.
(3) Benzene 1 exhibited the reactivity typical for the polyene rather than an aromatic compound. Thus, it was oxidized by m-CPBA and underwent Symmons-Smith reactions to give the corresponding all-cis tri-epoxide and tri-cyclopropane derivatives in high yields.
(4) Because of the annelation with strained BCH systems, naphthalene 3 readily underwent oxidation with air under irradiation of room light to give a novel macrocyclic alkyne having a two carbonyl groups and two cis-cyclobutane-1,4-diyl units. This was shown to be formed by retro[2+2+2] cleavage reaction of the endoperoxide first formed at the 1,4-positions of the BCH-annelated naphthalene. This is due to the high biradical character of naphthalene 3.
(5) A series of oligothiophenes (2-,3-,4-,6-, and 8-mers) completely surrounded by bicyclo[2.2.2]octene units were synthesized, and were converted to stable radical cation salts or dication salts, whose precise structures were determined by X-ray crystallography. These are considered as pertinent models for polaron or bipolaron of the p-doped states of oligothiophenes.

Report

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

    (25 results)

All 2005 2004 2003 2002 Other

All Journal Article (18 results) Publications (7 results)

  • [Journal Article] Synthesis and Properties of Cationic π-Conjugated Systeme Stabilized by Bicyclo[2.2.2]octene Units2005

    • Author(s)
      K.Komatsu, T.Nishinaga
    • Journal Title

      Synlett

      Pages: 187-202

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Persistent pi Radical Cations : Self-association and Its Steric Control in Condensed Phase2005

    • Author(s)
      T.Nishinaga, K.Komatsu
    • Journal Title

      Org.Biomol.Chem. 3

      Pages: 561-569

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Persistent pi Radical Cations : Self-association and Its Steric Control in Condensed Phase2005

    • Author(s)
      K.Komatsu, T.Nishinaga
    • Journal Title

      Org. Biomol. Chem. 3

      Pages: 561-569

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Crystal Structures and Spectroscopic Characterization of Radical Cations and Dications of Oligothiophenes Stabilized by Annelation with Bicyclo[2.2.2]octene Unit2004

    • Author(s)
      T.Nishinaga, A.Wakamiya, D.Yamazaki, K.Komatsu
    • Journal Title

      Journal of the American Chemical Society 126・10

      Pages: 3163-3174

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Radical Cation of Dibenzothiophene Fully Annelated with Bicyclo[2.2.2]octene Units : X-ray Crystal Structure and Electronic Propertis2004

    • Author(s)
      T.Yamazaki, T.Nishinaga, K.Komatsu
    • Journal Title

      Organic Letters 6

      Pages: 4179-4182

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Novel Cyclooctatetraene Radical Cation Planarized by Full Annelation with Bicyclo[2.2.2]octene2004

    • Author(s)
      T.Nishinaga, T.Uto, K.Komatasu
    • Journal Title

      Organic Letters 6

      Pages: 4611-4613

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Crystal Structures and Spectroscopic Characterization of Radical Cations and Dications of Oligothiophenes Stabilized by Annelation with Bicyclo[2.2.2] octene Unit2004

    • Author(s)
      T.Nishinaga, A.Wakamiya, D.Yamazaki, K.Komatsu
    • Journal Title

      Journal of the American Chemical Society 126-10

      Pages: 3163-3174

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Polymorphism and Stacking Disorder in Tris(bicyclo[2.1.1]hexeno)benzene2003

    • Author(s)
      H.Birkedal, H.-B.Biirgi, K.Komatsu, D.Schwarzenbach
    • Journal Title

      Journal of Molecular Structure 647

      Pages: 233-242

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Synthesis, Structure, and Dynamic Behavior of Cyclopentadienyl-lithium, -sodium, and -potassium Annelated with Bicyclo[2.2.2]octene Units : A Systematic Study on Site Exchange of Alkali Metals on a Cyclopentadienyl Ring in THF2003

    • Author(s)
      T.Nishinaga, D.Yamazaki, H.Stahr, A.Wakamiya, K.Komatsu
    • Journal Title

      Journal of the American Chemical Society 125・24

      Pages: 7324-7335

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Synthesis and Properties of Novel Oligothiophenes Surrounded by Bicyclo[2.2.2] octene Frameworks2003

    • Author(s)
      A.Wakamiya, D.Yamazaki, T.Nishinaga, T.Kitagawa, K.Komatsu
    • Journal Title

      The Journal of Organic Chemistry 68・22

      Pages: 8305-8314

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Synthesis, Structure, and Dynamic Behavior of Cyclopentadienyl-lithium, -sodium, and -potassium Annelated with Bicyclo[2.2.2]octene Units : A Systematic Study on Site Exchange of Alkali Metals on a Cyclopentadienyl Ring in THF2003

    • Author(s)
      T.Nishinaga, D.Yamazaki, H.Stahr, A.Wakamiya, K.Komatsu
    • Journal Title

      Journal of the American Chemical Society 125-24

      Pages: 7324-7335

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Synthesis and Properties of Novel Oligothiophenes Surrounded by Bicyclo[2.2.2]octene Frameworks2003

    • Author(s)
      A.Wakamiya, D.Yamazaki, T.Nishinaga, T.Kitagawa, K.Komatsu
    • Journal Title

      The Journal of Organic Chemistry 68-22

      Pages: 8305-8314

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] 1,2-Dithiin Annelated with Bicyclo[2.2.2]octene. One- and Two-Electron Oxidations and Formation of a Novel Tetrathiabicyclooctene Radical Cation with Remarkable Stability2002

    • Author(s)
      A.Wakamiya, T.Nishinaga, K.Komatsu
    • Journal Title

      Journal of the American Chemical Society 124・50

      Pages: 15038-15050

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Formation of a Novel Arenium Ion from the Radical Cation of a Twisted Triphenylene Fully Annelated with Bicyclo[2.2.2]octene Units2002

    • Author(s)
      T.Nishinaga, R.Inoue, A.Matsuura, K.Komatsu
    • Journal Title

      Organic Letters 4・9

      Pages: 1435-1438

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Radical Cation and Dication of Fluorene Fully Annelated with Bicyclo[2.2.2]octene Units : Importance of the Quinoidal Resonance Structure2002

    • Author(s)
      T.Nishinaga, R.Inoue, A.Matsuura, K.Komatsu
    • Journal Title

      Organic Letters 4・23

      Pages: 4117-4120

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] 1,2-Dithiin Annelated with Bicyclo[2.2.2]octene. One- and Two-Electron Oxidations and Formation of a Novel Tetrathiabicyclooctene Radical Cation with Remarkable Stability2002

    • Author(s)
      A.Wakamiya, T.Nishinaga, K.Komatsu
    • Journal Title

      Journal of the American Chemical Society 124-50

      Pages: 15038-15050

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Formation of a Novel Arenium Ion from the Radical Cation of a Twisted Triphenylene Fully Annelated with Bicyclo[2.2.2]octene Units2002

    • Author(s)
      T.Nishinaga, R.Inoue, A.Matsuura, K.Komatsu
    • Journal Title

      Organic Letters 4-9

      Pages: 1435-1438

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Radical Cation and Dication of Fluorene Fully Annelated with Bicyclo[2.2.2]octene Units : Importance of the Quinoidal Resonance Structure2002

    • Author(s)
      T.Nishinaga, R.Inoue, A.Matsuura, K.Komatsu
    • Journal Title

      Organic Letters 4-23

      Pages: 4117-4120

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Birkedal, H.-B.Burgi, K.Komatsu, D.Schwarzenbach: "Polymorphism and Stacking Disorder in Tris(bicyclo[2.1.1]hexeno)benzene"Journal of Molecular Structure. 647. 233-242 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Nishinaga, D.Yamazaki, H.Stahr, A.Wakamiya, K.Komatsu: "Synthesis, Structure, and Dynamic Behavior of Cyclopentadienyl-lithium, -sodium, and -potassium Annelated with Bicyclo[2.2.2]octene Units : A Systematic Study on Site Exchange of Alkali Metals on a Cyclopentadienyl Ring in THF"Journal of the American Chemical Society. 125・24. 7324-7335 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] A.Wakamiya, D.Yamazaki, T.Nisinaga, T.Kitagawa, K.Komatsu: "Synthesis and Properties of Novel Oligothiophenes Surrounded by Bicyclo[2.2.2]octene Frameworks"The Journal of Organic Chemistry. 68・22. 8305-8314 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Nishinaga, A.Wakamiya, D.Yamazaki, K.Komatsu: "Crystal Structures and Spectroscopic Characterization of Radical Cations and Dications of Oligothiophenes Stabilized by Annelation with Bicyclo[2.2.2]octene Unit"Journal of the American Chemical Society. 126・10. 3163-3174 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] A.Wakamiya, T.Nishinaga, K.Komatsu: "1,2-Dithiin Annelated with Bicyclo[2.2.2]octene. One-and Two-Electron Oxidations and Formation of a Novel Tetrathiabicyclooctene Radical Cation with Remarkable Stability"Journal of the American Chemical Society. 124・50. 15038-15050 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Nishinaga, R.Inoue, A.Matsuura K.Komatsu: "Formation of a Novel Arenium Ion from the Radical Cation of a Twisted Triphenylene Fully Annelated with Bicyclo[2.2.2]octene Units"Organic Letters. 4・9. 1435-1438 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Nishinaga, R.Inoue, A.Matsuura K.Komatsu: "Radical Cation and Dication of Fluorene Fully Annelated with Bicyclo[2.2.2]octene Units : Importance of the Quinoidal Resonance Structure"Organic Letters. 4・23. 4117-4120 (2002)

    • Related Report
      2002 Annual Research Report

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

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