• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Studies on the Active Molecules Prepared by Accumulation and Amplification of the Transannular Interaction between Chalcogen Atoms

Research Project

Project/Area Number 07404035
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

FURUKAWA Naomichi  University of Tsukuba, Department of Chemistry, Professor, 化学系, 教授 (80015966)

Co-Investigator(Kenkyū-buntansha) NABESHIMA Tatsuya  University of Tsukuba, Department of Chemistry, Associate Professor, 化学系, 助教授 (80198374)
Project Period (FY) 1995 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥34,800,000 (Direct Cost: ¥34,800,000)
Fiscal Year 1997: ¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 1996: ¥9,100,000 (Direct Cost: ¥9,100,000)
Fiscal Year 1995: ¥21,600,000 (Direct Cost: ¥21,600,000)
KeywordsTransannular Interaction / Dithia Dications / Hypervalent Compounds / 2-Center 2-Electron Bond / 3-Center 4-Electron Bond / Thiasulfonium Salts / S_Nl Reaction / Dealkylation / 脱アルチル化 / O,O'-ビフェニルジスルフィド / ジセレニド / 脱カルボニル / 光反応 / 渡環相互作用 / 高配位化合物 / ナフタレンジスルフィド
Research Abstract

In this studies, it was described the preparation of the dications having 2-center-2-electron [2c-2e] system and highcoordinated dications having 3-center-4-electron [3c-4e] bonds using organic compounds bearing multiple-chalcogen atoms arranged in space. The dications of [2c-2e] substituted by alkyl and benzyl groups at the chalcogen atoms were found to be quite reactive, and their formation was either undetected or detected only by low temperature ^1H-and ^<13>C-nmr spectroscopy. These dications once formed undergo facile dealkylation to afford N-alkyl acetamides which are trapped by CH_3CN used as a solvent together with thia-sulfonium salts in high yields. The mechanism for this dealkylation is rationally explained to proceed via an S_Nl-type substitution mechanism. On the other hand, the photolysis of the monooxides, mono-N-tosylsulfilimines and mono-S-ylides of naphtho [1,8-de] -1,3-dithiin provided the corresponding ketones, N-imines and olefins quantitatively. The photolysis re … More actions may proceed via the activation of the S-S interaction of these compounds. As to the highcoordinated [3c-4e] dication species, 1-phenyl 2,6-dimethylthiomethylphenyl tellurides were converted to the telluranes on oxidation. Similarly, 1,11-methanoseleno- [or-thio] diselenocin (or dithiocin) afforded the corresponding selenurane (or sulfurane) compounds on treatment of the diselenocin (or dithiocin) with one electron oxidant such as NOBF_4. These [3c-4e] hypervalent dications can be converted readily to the starting tris-selenides (or sulfides) by reducing the dications. In these oxidation-reduction reactions of the trisselenides (or sulfides), these compounds show molecular hysteresis during oxidation-reduction. The dications were stable enough to be isolated and their structures were determined by X-ray crystallographic analysis. The ab initio MO-calculation of these compounds reveal the charge-distribution among the atoms in the hypervalent molecules which was discussed with their reactivities. Less

Report

(4 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • Research Products

    (30 results)

All Other

All Publications (30 results)

  • [Publications] Naomichi, Furukawa・et al.: "Rearrangements of the Allyl Group in the Thermolysis of 1.8-Bis(allylthio)-and 1.8-Bis(allylseleno)naphthalene Monooxides via Through-space Interaction between Two Sulfur and Selenium Atoms." Tetrahedron. 51. 12239-12256 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi, Furukawa・et al.: "Mechanism for Photodecomposition of Naphto[1,8-de][1,3]dithiin-l-bis(ethoxycarbonyl)methylides." Tetrachedron Lett.36. 8039-8042 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi, Furukawa・et al.: "Evidence of Transannular Bonding Interaction between Two Sulfer Atoms on Photolysis of Naphtho[1,8-ef][1,4]dithiepins." J.Org.Chem.61. 6233-6239 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi, Furukawa・et al.: "First molecular and electronic structure determination of the dicationic salt of 1,11-(methanoselenomethano)-5H,7H-dibenzo[b,g][1,5]diselenocin by X-ray crystallographic analysis and ab initio calcuration." J.Chem.Soc.,Chem.Commun.1767-1768 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi, Furukawa・et al.: "Syntheses,Crystal Structure,and Reactivity of New Amino-and Ammonio-selenuranes Containing Transannular Se-N Bond from Ammonio-selenuranes Containing Transannular Se-N Bond from 5H,7H-Dibenzo[b,g][1,5]selenazocines." Tetrahedron. 54. 743-752 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi, Furukawa・et al.: "Molecular Activation of Organic Bis-Chalcogen Compounds via Thtough-Space and Through-Bond Interactions between Chalcogen Atoms." J.Synth.Org.Chem.,Jpn.55. 1006-1017 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi Furukawa et al.: "Rearrangements of the Allyl Group in the Thermolysis of 1,8-Bis (allylthio) - and 1,8-Bis (allylseleno) naphthalene Monooxides via Through-space Interaction between Two Sulfur and Selenium Atoms." Tetrahedron.51. 12239-12256 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi Furukawa et al.: "Mechanism for Photodecomposition of Naphto [1,8-de] [1,3] dithiin-1-bis (ethoxycarbonyl) methylides." Tetrahedron Lett.36. 8039-8042 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi Furukawa et al.: "Evidence of Transannular Bonding Interaction between Two Sulfur Atoms on Photolysis of Naphtho [1,8-ef] [1,4] dithiepins." J.Org.Chem.61. 6233-6239 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi Furukawa et al.: "First molecular and electronic structure determination of the dicationic salt of 1,11- (methanoselenomethano) -5H,7H-dibenzo [b, g] [1,5] diselenocin by X-ray crystallographic analysis and ab initio calculation." J.Chem.Soc., Chem.Commun.1767-1768 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi Furukawa et al.: "Synthesis, Crystal Structure, and Reactivity of New Amino-and Ammonio-selenuranes Containing Transannular Se-N Bond from Ammonio-selenuranes Containing Transannular Se-N Bond from 5H,7H-Dibenzo [b, g] [1,5] selenazocines." Tetrahedron. 54. 743-752 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi Furukawa et al.: "Molecular Activation of Organic Bis-Chalcogen Compounds via Through-Space and Through-Bond Interactions between Chalcogen Atoms." J.Synth.Org.Chem., Jpn.55. 1006-1017 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Naomichi Furukawa et al.: "Isolation and Structure of Bis(2,2'-biphenylylene)dichloro-,and-difluoropertellurane,[12-Te-6(C4X2),X=Cl,F](λ^6-Tellane)" Organometallics. 15. 3256-3258 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Simple Procedure for the Synthesis of 2,5-Disilylated Thiophene S-Oxides with m-Chloroperbenzoic Acid in the Presence of BF_3(Et_2O)" Heterocycles,. 44. 61-66 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Isolation and X-ray Structure Determination of New Tellurane Te-oxide Dimer[12-Te-6(C4O2)]_2(λ^6-Tellane)" J.Organomet.Chem.543. 77-82 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "A One Step Conversion of Sulfoxides to Aldehydes by the Neighboring Group Participation in the Pummerer Rearrangement of Ortho-hydroxymethyl Aryl Benzyl Sulfoxide" Heterocycles,. 46. 177-184 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "First Isolation of Bis (2,2'-biphenylylene)sulfuranyl Bis(tetrafluoroborate)[8-S-4(C4)]^<2+>" J.Am.Chem.Soc.119. 12374-12375 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Naomichi Furukawa et al.: "Exclusive cis-1,4-Addition Reaction in the Bromination of 2,5-Bis(trimethylsilyl)thiophene Monooxide" Heterocycles. 48. 227-234 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Fujii,H.Kusanagi,and N.Furukawa: "Mechanism for Photodecomposition of 4,8,10-Trithiadibenzo [cd,ij] -azulene-8-oxides" Chemistry Letters. 655-656 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Fujii,O.Takahashi,and N.Furukawa: "Evidence of Transannular Bonding Interaction between Two Sulfur Atoms on Photolysis of Naphtho [1,8-ef] [1,4] dithiepins" J.Org.Chem. 61. 6223-6239 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Takaguchi,E.Horn and N.Furukawa: "Preparation and X-ray Structure Analysis of 1,1,5,5,9,9-Hexachloro-1,5,9-tritellurocyclododecane(C16([12]ane Te3)),and Its Redox Behavior" Organometallics. 15. 5112-5115 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Sato,T.Yamashita,E.Horn,and N.Furukawa: "Isolation and Structure of Bis(2,2'-biphenylylene)dichloropertellurane,[12-Te-6(C4C12)](λ6-Tellane)" Organometallics. 15. 3526-3528 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] A.B.Bergholdt,E.Horn.O.Takahashi S.Sato.K.Kobayashi,N.Furukawa: "Crystal Structure and Initio Calculation of a New Dicationic Tellurane(λ4-Tellane) : A Positively Charged Hypervalent Bonding System" J.A.C.S. (in press).

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Shima,R.Kobayashi,T.Nabeshima,and N.Furukawa: "Activation and Facile Dealkylation of Monooxides of 2.2'-Bis(alkylthio)biphenyl with Triflic Anhydride Salts" Tetrahedron Letters. 37. 667-670 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Naomichi Furukawa: "Activation and Facile Dealkylation of Monooxides of 2,2′-Bis (alkylthio) biphenyl with Triflic Anhydride Salts" Tetrahedron Lett.37. 667-670 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Naomichi Furukawa: "Mechanism for photodecomposition of Naphtho [1,8-de][1,3] dithiin-1-bis (ethoxycarbonyl) methylides : A Convenient Method for Preparation of Electron-DeficientOlefins" Tetrahedron Lett.36. 8039-8042 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Naomichi Furukawa: "Rearrangements of the Allyl Group in the Thermolysis of 1,8-Bis (allylthio) and bis (allylseleno) naphthalene Monooxides via Through-space Interaction between Two Sulfur and Selenium Atoms" Tetrahedron Lett.51. 12239-12256 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Naomichi Furukawa: "The Pummerer and the Thio-Claisen-type Rearrangements of Naphtho [1,8-bc]-1,5-dithiocin Monooxide and N-p-Tosvlsulfilimine" Heteroatom Chemistry. 6. 559-565 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Naomichi Furukawa: "One-Pot Diels-Alder Reaction of N-p-Tosylsulfilimines Generated by BF_3-Et_2O Catalyzed Transformation of Naphtho[1,8-de]dithiin-1-N-p-Tosylsulfilimines" Tetrahedron Lett.36. 4813-4816 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Naomichi Furukawa: "Preparation of N-p-Tosylsulfilimines by the Intramolecular Photo-Imino Group Migration of Naphtho [1,8-de] dithiin-N-p-Tosylsulfilimines" Tetrahedron Lett.36. 1075-1078 (1995)

    • Related Report
      1995 Annual Research Report

URL: 

Published: 1995-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi