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2002 Fiscal Year Final Research Report Summary

Development of Novel Molecular Functions of γ-Cyclodextrin-Bicapped C60 Supramolecular Complex and Supermacroheterocyccs with C60

Research Project

Project/Area Number 13305062
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

UEMURA Sakae  Faculty of Engineering, Professor, 工学研究科, 教授 (70027069)

Co-Investigator(Kenkyū-buntansha) TAKEKUMA Shin-ichi  Kinki University, Associate Professor, 理工学部, 助教授 (00171629)
NISHIMURA Takahiro  Faculty of Engineering, Research Associate, 工学研究科, 助手 (50335197)
NISHIBAYASHI Yoshiaki  Faculty of Engineering, Research Associate, 工学研究科, 助手 (40282579)
YAMAGUCHI Yoshihiro  Kinki University, Lecturer, 理工学部, 講師 (30200637)
Project Period (FY) 2001 – 2002
Keywordsfullerene / cyclodextrin / large-membered ring compound / asymmetric reduction / nitrogen fixation / ammonia / heteroatom / inclusion compound
Research Abstract

Since the first prediction of the existence of C_<60>(buckminsterfullerence) molecule with soccerball structure based on the superaromaticity concept, we have been interested in the reactivities and function of C_<60> and its derivatives. We have designed and succeeded in preparing and characterizing the water-soluble C_<60>/γ-cyclodextrin (1:2) complex (γ-cyclodextrin-bicapped C_<60>) by the inclusion of C_<60> with γ-cyclodextrin at 118 degrees Celsius for 114 h in H_20/toluene. During our study, we have found novel functions of γ-cyclodextrin-bicapped C_<60> for asymmetric reduction of ketenes and nitrogen fixation of molecular N_2 into ammonia.
γ-Cyclodextrin-bicapped C_<60> mediates asymmetric reduction of prochiral alkyl aryl ketonxes using NaBH_4 as a reducing reagent to afford the corresponding chiral sec-alcohols with moderate enantioselectivity.
Treatment of γ-cyclodextrin-bicapped C_<60> with an excess amount of sodium hydrosulfite under 1 atom of N_2 at 60 degrees Celsius for 1 h gives ammonia in moderate yield. We consider that the coordinated N_2 on the C_<60> molecular surface in γ-cyclodextrin-bicapped C_<60> is transformed into ammonia. Ammonia is also obtained in a lower yield with dilute H_2SO_4 under similar reaction conditions. In both cases, no formation of ammonia is observed in the absence of either N_2 or γ-cyclodextrin-bicapped C_<60>. This remarkable result may be the first example of the transformation of N_2 gas into ammonia by using only carbon, hydrogen, and oxygen elements.

  • Research Products

    (60 results)

All Other

All Publications (60 results)

  • [Publications] Nobuyuki Kakiuchi et al.: "Pd(II)-Hydrotalcite-Catalyzed Oxidation of Alcohols to Aldehydes and Ketones Using Atmospheric of Air"J.Org.Chem.. 66. 6620-6625 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yasunari Maeda et al.: "Oxovanadium Complex-Catalyzed Oxidation of Propargylic Alcohols Using Molecular Oxygen"Tetrahedron Lett.. 42. 8877-8879 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takahiro Nishimura et al.: "Palladium-Catalyzed Asymmetric Arylation of tert-Cyclobutanols via Enantioselective C-C Bond Cleavage"Chem.Commun.. 50-51 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takahiro Nishimura et al.: "Palladium-Catalyzed Kinetic Resolution of tert-Cyclobutanols via C-C Bond Cleavage"Tetrahedron Lett.. 43. 3037-3039 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshihiro Miyake et al.: "Kinetic Resolution of Secondary Alcohols via Chiral Pd(II)-Complex-Catalysed Enantioselective Benzolylation Using CO and Organobismuth(V) Compound"Chem.Commun.. 2584-2585 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshihiro Miyake et al.: "Asymmetric Synthesis of Epoxides from Aromatic Aldehydes and Benzyl Halides Catalyz by Optically Active Sulfides Having Binaphthyl Skeleton"Heteroatom Chem.. 13. 270-275 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Toshiyuki Ohe et al.: "Palladium(II)-and Rhodium(III)-Catalyzed Carbonylation Reaction of Aryltin Compounds"Bull.Chem.Soc.Jpn.. 74. 1343-1348 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Toshiyuki Ohe et al.: "A Novel Catalytic Activity of Bismuth(III) Salts in Palladium(II)-Catalyzed Atom Economical_Michael-Type Hydroarylation of Nitroalkenes with Aryltin Compounds"Tetrahedron Lett.. 43. 1269-1271 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Propargylic Alkylation of Propargylic Alcohols with Ketones : Straightforward Synthesis of γ-Keto Acetylenes"J.Am.Chem.Soc.. 123. 3393-3394 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Izuru Takei et al.: "Ruthenium-Catalyzed Asymmetric Hydrosilylation of Ketoximes Using Chiral Oxazolinylferrocenylphosphines"Chem.Commun.. 2360-2361 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshihiro Yamaguchi et al.: "Creation of Nanoscale Oxaarenecyclynes and Their C_<60> Complexes"Tetrahedron Lett.. 43. 3277-3280 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Shigeya Kobayashi et al.: "Shape-Persistent Cyclyne-type Azamacrocyclcs : Synthesis, Unusual Light-Emitting Characteristics, and Specific Recognition of the Sb(V) Ion"Tetrahedron Lett.. 44. 1469-1472 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Shigeya Kobayashi et al.: "Synthesis and Properties of Novel Thiaarenecyclynes"Tetrahedron Lett.. 44. 1807-1810 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yasumari Maeda et al.: "Oxovanadium Complex-Catalyzed Aerobic Oxidation of Propargylic Alcohols"J.Org.Chem.. 67. 6718-6724 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshihiro Miyake et al.: "Asymmetric Baeyer-Villiger Oxidation of Cyclic Ketones Using Chiral Organoselenium Catalysts"Bull.Chem.Soc.Jpn.. 75. 2233-2237 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Tomochika Iwata et al.: "Palladium(II) Complex-Catalysed Enantioselective Benzolylation of Alcohols Using Carbon Monoxide and Organobismuth(V) Compound"J.Chem.Soc., Perkin Trans.1. 1548-1554 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshihiro Miyake et al.: "Kinetic Resolution of Racemic Ferrocenylphosphine Compounds Using Optically Active Cyclic Selenoxides as Oxidants"Phosphorus, Sulfur, and Silicon. 177. 2107-2108 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Toshiyuki Ohe et al.: "A Novel Catalytic Activity of Bismuth(III) Salts in Palladium(II)-Catalyzed Atom Economical Michael-Type Hydroarylation of Nitroalkenes with Aryltin Compound"Tetrahedron Lett.. 43. 1269-1271 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Novel Ruthenium-and Platinum-Catalyzed Sequential Reactions : Synthesis of Substituted Furans and Pyrroles from Propargylic Alcohols and Ketones"Angew.Chem.Int.Ed.. 42(印刷中). (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Shin-ichi Takekuma et al.: "A Facile Preparation of 5-Isopropylidene-3,8-dimethyl-1(5H)-azulenone and its Crystal Structure"Bull.Chem.Soc.Jpn.. 75. 151-152 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Shin-ichi Takekuma et al.: "An Efficient Preparation, the Structure and the Properties of 1-Isopropyl-4-(3-guaiazulenylmethylium)benzene Hexafluorophosphate and Tetra-fluoroborate"Tetrahedron Lett.. 44. 2073-2078 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masato Sasaki et al.: "The Crystal Structure and Characteristic Chemical Property of 1,2-Bis(3-guaiazulenylmethylium)benzene Bishexafluorophosphate"Tetrahedron Lett.. 44. 275-279 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masato Sasaki et al.: "A Facile Preparation, the Crystal Structure, the Chemical and Electrochemical Properties of [4-(Dimethylamino)phenyl]-3-guaiazulenylmethylium Tetrafluoroborate"Tetrahedron. 59. 505-516 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Toshiyuki Ohe et al.: "Palladium(II)-Catalyzed Michael-Type Hydroarylation of Nitroalkenes Using Aryltins and Sodium Tetraarylborates"Bull.Chem.Soc.Jpn.. 76(印刷中). (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshihiro Miyake et al.: "Kinetic Resolution of Racemic Ferrocenylphosphine Compounds Using Optically Active Cyclic Selenoxides as Oxidants"Bull.Chem.Soc.Jpn.. 76. 382-387 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Cycloaddition of Propargylic Alcohols with Phenol Derivatives via Allenylidene Intermediates : Catalytic Use of the Allenylidene Ligand as C_<3> Unit"J.Am.Chem.Soc.. 124. 7900-7901 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Propargylation of Aromatic Compounds with Propargylic Alcohols"J.Am.Chem.Soc.. 124. 11846-11847 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Youichi Inada et al.: "Ruthenium-Catalyzed Propargylic Substitution Reaction of Propargylic Alcohols with Thiols : A General Synthetic Route to Propargylic Sulfides"J.Am.Chem.Soc.. 124. 15172-15173 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Synthesis of Diruthenium Complexes Containing Chiral Thiolate-Bridged Ligands and Their Application to Catalytic Propargylic Alkylation of Propargylic Alcohols with Acetone"Organometallics. 22. 873-876 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Propargylation of Aromatic Compounds with Propargylic Alcohols Catalyzed by Cationic Diruthenium Complex"Angew.Chem.Int.Ed.. 42(印刷中). (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nobuyuki Kakiuchi et at.: "Pd(II)-Hydrotalcite-Catalyzed 0xidation of Alcohols to Aldchydes and Ketenes Using Atmospheric of Air"J. Org. Chem.. 66. 6620-6625 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yasunari Maeda et al.: "Oxovanadium Complex-Catalyzed Oxidation of Propargylic Alcohols Using Mojecular Oxygen"Tetrahedron Lett.. 42. 8877-8879 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takahiro Nishimura et al.: "Palladium-Catalyzed Asynxmetric Arylation of tert-Cyclobutanols via Enantioseleclive C-C Bond Cleavage"Chem. Common.. 50-51 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takahiro Nishintura et al.: "Palladium-Catalyzed Kinetic Resolution of tert-Cyclobutanols via C-C Bond Cleavage"Tetrahedron Lett.. 43. 3037-3039 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshihiro Miyake et al.: "Kiutetic Resolution of Secondary Alcohols via Choral Pd(II)-Complex-Catalysed Enantioselective Benzolyation Using CO and Organobismuth(V) Compound"Chem. Common.. 2584-2585 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshihiro Miyake et al.: "Asymrnetric Synthesis of Epoxides from Aromatic Aldehydes and Benzyl Halides CataTyzed by 0ptically Active Sulfides Having Binaphthyl Skeleton"Heteroatont Chem.. 13. 270-275 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Toshiyuki Ohe et al.: "Palladium(II)- and Rhodium(III)-Catalyzed Carbonylation Reaction of Aryltin Compounds"Bull. Chem. Soc. Jpn.. 1343-1348 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Toshiyuki Ohe at al.: "A Novel Catalytic Activity of Bismuth(III) Salts in Palladium(II)-Catalyzed Atom Economical Michael-Type Hydroarylation of Nitroalkenes with Aryltin Compounds"Tetrahedron Lett.. 43. 1269-1272 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshiaki Nishibayashi et at.: "Ruthenium-Catalyzed Propargylic Propargylie of Propargylic Alcohols with Ketenes: Straightforward Synthesis of γ-Kcto Acetylenes"J. Am. Chem. Soc.. 123. 3393-3394 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] lzuru Takei et al.: "Ruthenium-Catalyzed Asymmetric Hydrosilylation of Ketoximes Using Choral Oxazolinylferrocenylphosphines"Chem. Commun.. 2360-2361 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshihiro Yamaguchi at al.: "Creation of Nanoscale Oxaarenecyclynes and Their C_<60> Complexes"Tetrahedron Left.. 43. 3277-3280 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shigeya Kobayashi et al.: "Shape-Persistent Cyclync-type Azamacrocycles: Synthesis, Unusual Light-Emitting Characteristics, and Specific Recognition of the Sb(V) Ion"Tetrahedron Lett.. 44. 1469-1472 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shigeya Kobayashi et al.: "Synthesis and Propcrties of Novel Thiaarenecyclynes"Tetrahedron Lett.. 44. 1807-1810 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yasumari Maeda el al.: "Oxovanadium Complex-Catalyzed Aerobic Oxidation of Propargylic Alcohols"J. Org. Chem.. 67. 6718-6724 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshihiro Miyake et al.: "Asymmetric Baeyer-Villiger Oxidation of Cyclic Ketones Using Chiral Organoselenium Catalysts"Bull. Chem. Soc. Jpn.. 75. 2233-2237 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Tomochika Iwata et al.: "Palladium(II) Complex-Catalyzed Enantiosclective Benzolylation of Alcohols Using Carbon Monoxide and Organobismnuth(V) Compound"J. Chem. Soc. , Perkin Trans.. I. 1548-1554 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshihiro Miyake et al.: "Kinetic Resolution of Racemic Ferroccmtylpltosphine Compounds Using Optically Active Cyclic Selemtoxides as Oxidamats"Phosphorus, Sulfur, and Silicon. 177. 2107-2108 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Toshiyuki Ohe at al.: "A Novel Catalytic Activity of Bismuth(III) Salts in Palladium(II)-Catalyzed Atom Econonical Michael-Type Hydroarylation of Nihoalkcnes with Aryltin Compounds"Tetrahedron Lett.. 43. 1269-1271 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshihiro Miyake et al.: "Kinetic Resolution of Racentic Ferrocenylphosphine Compounds Using Optically Active Cyclic Selenoxidcs as Oxidants"Bull. Chem. Soc. Jpn.. 76. 382-387 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Cycloaddition of Propargylic Alcohols with Phenol Derivatives via Allenylidene Intermediates: Catalytic Use of the Allenylidene Ligand as C_3 Unit"J. Am. Chem. Soc.. 124. 7900-7901 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Propargylation of Aromatic Compounds with Propargylic Alcohols"J. Am. Chem. Soc.. 124. 11846-11847 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Youichi lnada et al.: "Ruthetxium-Catalyzed Propargylic Substitution Reaction of Propargylic Alcohols with Thiols: A General Synthetic Route to Propargylic Sulfides"J. Am. Chem. Soc.. 124. 15172-15173 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshiiaki Nishibayashi at al.: "Synthesis of Diruthenium Complexes Containing Chiral Thiolate-Bridged Ligands and Their Application to Catalytic Propargylic Alkylation of Propargylic Alcohols with Acetone"Oroanonaetallics. 22. 873-876 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Propargylation of Aromatic Compounds with Propargylic Alcohols Catalyzcd by Cationic Diruthenium Complex"Angew. Chem. Int. Ed.. in press.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshiaki Nishibayashi et al.: "Novel Ruthenium and Platinum-Catalyzed Scquential Reactions: Synthesis of Substituted Furans and Pyrroles from Propargylic Alcohols and Ketrones"Angew. Chem. Int. Ed.. in press.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shin-ichi Takekuma et al.: "A Facile Preparation of 5-Isopropylidene-3,8-dimenthyl-I(5H)-azulenone and its Crystal Structure"Bull. Chem. Soc. Jpn.. 75. 151-152 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shin-ichi Takekumura et al.: "An Efficicnt Preparation, the Strtrcture and the Properties of 1-lsopropyl-4-(3-guaiazulenylmethylium)benzene Hexafluoroplcosphate and Tetra-fluoroborate"Tetrahedron Lett.. 44. 2073-2078 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masato Sasaki et al.: "The Crystal Structure and Characteristic Chemical Property of 1, 2-Bis(3-guaiazulenylmethylium)benzene Bishexafluorophosplcate"Tetrahedron Lett.. 44. 275-279 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masato Sasaki et al.: "A Facile Preparation, the Crystal Structure, the Chemical and Electrochemical Properties of [4-(Dimethylamino)phenyl]-3-guaiazulenylmethylium Tetrafluoroborate"Tetrahedron. 59. 505-516 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Toshiyuki Ohe et al.: "Palladium(II)-Catalyzed Michael-Type Hydroarylatiotn of Nitroalkenes Using Aryltins and Sodium Tetraarylborates"Bull. Chem. Soc. Jpn.. in press.

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

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Published: 2004-04-14  

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