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1991 Fiscal Year Final Research Report Summary

Molecular Transformation Based on Design of Novel Reaction Environment

Research Project

Project/Area Number 02303003
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionThe University of Tokyo

Principal Investigator

OKAZAKI Renji  Faculty of Science, University of Tokyo, Professor, 理学部, 教授 (70011567)

Co-Investigator(Kenkyū-buntansha) TOMIOKA Hideo  Faculty of Engineering, Mie University, Professor, 工学部, 教授 (20024599)
TAKAYA Hidemasa  Faculty of Engineering, Kyoto University, Professor, 工学部, 教授 (40022644)
KOBAYASHI Keiji  Faculty of Arts and Sciences, University of Tokyo, Professor, 教養学部, 教授 (50012456)
UNEYAMA Kenji  Faculty of Engineering, Okayama University, Professor, 工学部, 教授 (00033150)
AOYAMA Yasuhiro  Department of Chemistry, Nagaoka University of Technology, Professor, 工学部, 教授 (00038093)
Project Period (FY) 1990 – 1991
KeywordsMolecular transformation / Reactive environment / Crystalline field reaction / Matrix / Inclusion Crystal / Transition metal complex / Silicon cluster / Steric protection
Research Abstract

The present co-operative research has been carried out by the following four groups : (1)molecular transformation based on the design of novel monomolecular environment, (2)molecular transformation based on the design of novel multimolecular environment, (3)molecular transformation based on the design of novel biological model system, and(4)theoretical consideration of the design of novel molecular environment. Group 1 studied the reactions of alpha-oxoamides, . acetylenes, cyclohexenone, tropothione in liquid crystals or crystals, and revealed the possible unique reactions in ordered systems like liquid crystals or crystals. Group 2 studied multipoint interaction in porphyrin derivatives, photosynthesis and visual system model, and epoxidation as an oxygenase model. Group 3 studied the reactions of carbenes or active oxygen species in cryogenic matrices, unique trifluoromethylation by electrolysis, the design of extremely bulky substituent as a unique molecular environment, and, chiral catalyst by BINAP-RU complexes. These results suggest that well-designed monomolecular systems can provide unique molecular environment. Group 4 studied the improvement of X-ray crystallographic analysis system, thus enabling very fact measurement of cystallographic data for crystalline phase reactions. Theoretical studies on some silicon clusters like Si_<60>, Si_<24>, Si_<6O>H_<60> were carried out to reveal interesting differences between the silicon and carbon clusters.

  • Research Products

    (44 results)

All Other

All Publications (44 results)

  • [Publications] N.Tokitoh,H.Suzuki,T.Matsumoto,Y.Matsuhashi,and R.Okazaki: "1,2,3,4,5-Tetrathiametallolanes of Group 14 Metals,RR'MS_4(M=Si,Ge,and Sn):Synthesis and Crystal Structures." J.Am.Chem.Soc.113. 7047-7049 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Sakamoto,S.Watanabe,T.Fujita,H.Aoyama,and Y.Omote: "Rhotochemical Reactions of N-Acyldithiocarbamates and N-Acylthio-carbamates." J.Chem.Soc.Perkin Trans.1. 2541-2545 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Motomutra and Y.Aoyama: "Accumulation of Hydrogen-Bonding and Electrostatic Binding Sites:Stabilization of Salts in Hydroxylic Media via Intramolecular Hydrogen-Bonding." J.Org.Chem.56. 7224-7228 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Akasaka,K.Sato,M.Kako,and W.Ando.: "Formation of 1,2,3,6-Dioxadisilene in Photo-induced Electron Transfer Oxygenation of 1,2-Disiletene." Terahedorn Lett.32. 6605-6608 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Sakurada,M.Kajitani,K.Dohki,T.Akiyama,and A.Sugimori: "Reactions of Dithiolenes with Diazo Compounds:Cycloaddition and Dissociation of Alkylidene Groups." J.Organomet.Chem.423. 141-161 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Uneyama and M.Kanai: "Generation of Perfluoroalkyl Radicals at Low Temporature by Tellurolate Meiated Electron Transfer." Tetrahedron Lett.32. 7425-7428 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.T.Osano,A.Uchida,and Y.Ohashi: "Optical Enrichment of a Racemic Chiral Crystal by X-ray Irradiation." Nature (London). 352. 510-512 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kira,T.Maruyama,and H.Sakurai: "The First Matrix-Isolation and Electronic Structure of Vinyl-Substituted Silylenes." Tetrahedron Lett.33. 243-246 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Mazaki,S.Murata,and K.Kodayashi: "Thermal and Photochemical Formation of Quinonoid Derivatives of Condensed Polythiophenes and Their Spectral Properties." Tetrahedeon Lett.32. 4367-4370 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Sakata,H.Tsue,Y.Goto,S.Misumi,T.Asahi,T.Nishikawa,T.Okada,N.Mataga: "Observation of Large Orientation effect on Photoinduced Electron Transfer in Rigid Porphyrin-Quinone Compounds." Chem.Lett.1991. 1307-1310 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] R.Akaba,H.Sakuragi,and K.Tokumaru: "Detection of Dimeric Cation Racicals of Trans-stilbene in 2,4,6-triphenylpyrylium Tetrafluoroborate-sensitized Electron Transfer Reactions in Dichotomethane." Chem.Phys.Lett.174. 80-84 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Miyazaki,A.Izuoka,and T.Sugawara: "Structure of 11,12-Bis(diazo)-11,12-dihydroindeno〔2,1-a〕fluorene" Acta Cryst.C47. 1054-1056 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] X.Zhang,K.Mashima,K.Koyano,M.Sayo,H.Kumobayashi,S.Akutagawa,and H.Takaya: "Synthesis of Partially Hydrogenated BINAP Variants." Tetrahedron Lett.32. 7283-7286 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] F.Toda and K.Tanaka: "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 Compounds." J.Org.Chem.56. 7332-7335 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Yoneda,K.Tsujimoto,M.Ohashi,M.Shiratsuchi,Y.Ohkawa,and K.Isa: "Fast Atom Bombardment Mass Spectra of the β-Blocker Nipradilol with Nitratye Ester Group-Tandem Mass Spectrometory (MS/MS) and B/E Constant Linked Scanning." Chem.Pharm.Bull.38. 3389-3394 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Murata and H.Tomioka: "Photochemistry of o-Nitrophenylazide in Matrices.The First Direct Spectroscopic Observation of O-Dinitrosobenzene." Chem.Lett.1992. 57-60 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Iwaoka and S.Tomoda: "Direct Observation of Intramolecular Interaction Between a Divalent Selenium and a tertiary Amine by Means of Single Crystal X-ray Analysis and NMR Spectroscopy." Phosphorus,Sulfer,and Silicon and The Related Elements.

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Nagase and K.Kobayashi: "Si_<60> and Si_<60>X (X=Ne,F^-,and Na^+)" Chem.Phys.Lett.187. 291-294 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Nishino,M.Takagi,T.Kawata,I.Murata,J.Inanaga,and K.Nakasuji: "Thiepin-iron Tricarbonyl:Stabilization of Thermally Labile Parent Thiepin by Transition Metal Complexzation." J.Am.Chem.Soc.113. 5059-5060 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Nakamura and N.Nakamura: "Spin State and Rotational Orientation of Iron Porphyrin Complexes with Hindered 2-Methylbenzimidazole as Axial Ligands." Chem.Lett.1991. 1885-1888 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Natuta and K.Maruyama: "High Oxygen-Evolving Activity of Rigidly Linked Manganese (III)Porphytin Dimers.A Functional Model of Mangenese Catalase." J.Am.Chem.Soc.113. 3595-3596 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Machiguchi,Y.Kano,and T.Hasegawa: "General and Facile Synthesis of 2-Substituted Tropothiones." Chem.Lett.1990. 1563-1566 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N. Tokitoh, H. Suzuki, T. Matsumoto, Y. Matsuhashi, and R. Okazaki: "1, 2, 3, 4, 5-Tetrathiametallolanes of Group 14 Metals, RR'MS_4 (M=Si, Ge, and Sn) : Synthesis and Crystal Structures." J. Am. Chem. Soc.113. 7047-7049 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Sakamoto, S. Watanabe, T. Fujita, H. Aoyama, and Y. Omote: "Photochemical Reactions of N-Acyldithiocarbamates and N-Acylthiocarbamates." J. Chem. Soc. Perkin Trans.1. 2541-2545 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Motomura and A. Aoyama: "Accumulation of Hydrogen-Bonding and Electrostatic Binding Sites : Stabilization of Salts in Hydroxylic Media via Intramolecular Hydrogen-Bonding." J. Org. Chem.56. 7224-7228 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Akasaka, K. Sato, M. Kako, and W. Ando: "Formation of 1, 2, 3, 6-Dioxadisilene in Photo-induced Electron Transfer Oxygenation of 1, 2-Disiletene." Tetrahedron Lett.32. 6605-6608 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Sakurada, M. Kajitani, K. Dohki, T. Akiyama, and A. Sugimori: "Reactions of Dithiolenes with Diazo Compounds : Cycloaddition and Dissociation of Alkylidene Groups." J. Organomet. Chem.423. 141-161 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Uneyama and M. Kanai: "Generation of Perfluoroalkyl Radicals at Low Temperature by Tellurolate Mediated Electron Transfer." Tetrahedron Lett.32. 7425-7428 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. T. Osano, A. Uchida, and Y. Ohashi: "Optical Enrichment of a Racemic Chiral Crystal by X-ray Irradiation." Nature (London). 352. 510-512 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Kira, T. Maruyama, and H. Sakurai: "The First Matrix-Isolation and Electronic Structure of Vinyl-Substituted Silylenes." Tetrahedron Lett.33. 243-246 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Mazaki, S. Murata, and K. Kobayashi: "Thermal and Photochemical Formation of Quinonoid Derivatives of Condensed Polythiophenes and Their Spectral Properties." Tetrahedron Lett.32. 4367-4370 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Sakata, H. Tsue, Y. Goto, S. Misumi, T. Asahi, T. Nishikawa, T. Okada, and N. Mataga: "Observation of Large Orientation Effect on Photoinduced Electron Transfer in Rigid Porphyrin-Quinone Compounds." Chem. Lett.1307-1310 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] R. Akaba, H. Sakuragi, and K. Tokumaru: "Detection of Dimeric Cation Radicals of Trans-stilbene in 2, 4, 6triphenylpyrylium Tetrafluoroborate-sensitized Electron Transfer Reactions in Dichloromethane." Chem. Phys. Lett.174. 80-84 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A. Miyazaki, A. Izuoka, and T. Sugawara: "Structure of 11, 12-Bis (diazo) -11, 12-dihydroindeno [2, 1-a] fluorene" Acta Cryst.C47. 1054-1056 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] X. Zhang, K. Mashima, K. Koyano, N. Sayo, H. Kumobayashi, S. Akutagawa, and H. Takaya: "Synthesis of Partially Hydrogenated BINAP Variants." Tetrahedron Lett.32. 7283-7286 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F. Toda and K. Tanaka: "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 Compounds." J. Org. Chem.56. 7332-7335 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Yoneda, K. Tsujimoto, M. Ohashi, M. Shiratsuchi, Y. Ohkawa, and K. Isa: "Fast Atom Bombardment Mass Spectra of the beta-Blocker Nipradilol with Nitrate Ester Group-Tandem Mass Spectrometry (MS/MS) and B/E Constant Linked Scanning." Chem. Pharm. Bull.3389-3394 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Murata and H. Tomioka: "Photochemistry of o-Nitrophenylazide in Matrices. The First Direct Spectroscopic Observation of o-Dinitrosobenzene." Chem. Lett.57-60 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Iwaoka and S. Tomoda: "Direct Observation of Intramolecular Interaction Between a Divalent Selenium and a tertiary Amine by Means of Single Crystal X-ray Analysis and NMR Spectroscopy." Phosphorus, Sulfur, and Silicon and The Related Elements.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Nagase and K. Kobayashi: "Si_<60> and Si_<60>X (X=Ne, F^-, and Na^+)" Chem. Phys. Lett.187. 291-294 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Nishino, M. Takagi, T. Kawata, I. Murata, J. Inanaga, and K. Nakasuji: "Thiepin-iron Tricarbonyl : Stabilization of Thermally Labile Parent Thiepin by Transition Metal Complexization." J. Am. Chem. Soc.113. 5059-5060 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Nakamura and N. Nakamura: "Spin State and Rotational Orientation of Iron Porphyrin Complexes with Hindered 2-Methylbenzimidazole as Axial Ligands." Chem. Lett.1885-1888 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Naruta and K. Maruyama: "High Oxygen-Evolving Activity of Rigidly Linked Manganese (III) Porphyrin Dimers. A Functional Model of Manganese Catalase." J. Am. Chem. Soc.113. 3595-3596 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Machiguchi, Y. Kano, and T. Hasegawa: "General and Facile Synthesis of 2-Substituted Tropothiones." Chem. Lett.1563-1566 (1990)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1993-03-16  

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