2002 Fiscal Year Annual Research Report

バイキャップ型及び土星型フラーレン超分子錯体の創製と新機能開発

Research Project

Project/Area Number	13305062
Research Institution	KYOTO UNIVERSITY
Principal Investigator	植村榮京都大学, 工学研究科, 教授 (70027069)
Co-Investigator(Kenkyū-buntansha)	武隈真一近畿大学, 理工学部, 助教授 (00171629) 西村貴洋京都大学, 工学研究科, 助手 (50335197) 西林仁昭京都大学, 工学研究科, 助手 (40282579) 山口仁宏近畿大学, 理工学部, 講師 (30200637)
Keywords	フラーレン / シクロデキストリン / 大環状化合物 / 不斉還元 / 窒素固定 / アンモニア / ヘテロ元素 / 包接化合物
Research Abstract	γ-シクロデキストリンまたはヘテロ原子を持つ超大環状化合物とフラーレン(C_<60>)とから合成できる安定なバイキャップ型及び土星型超分子錯体を合成・単離し、フラーレンには見られないユニークな物性・機能を解明することを目的として以下の研究を行った。 C_<60>とγ-シクロデキストリンとから合成できるバイキャップ型C_<60>錯体(1)に窒素分子が配位し活性化されていることは、赤外吸収スペクトル、熱重量及び示差熱分析等により確認されている。これらの研究背景を基に、1を用いた窒素固定を検討した。1と過剰量の還元剤である次亜硫酸ナトリウムとを60℃で1時間反応させた結果、1を基準にして最高33%の収率でアンモニアが生成していることが確認された。本反応で生成したアンモニアは化学量論量に過ぎないが、この研究成果は、金属を用いずに、炭素、酸素及び水素とからなる1を用いて窒素固定に成功した世界最初の例である。また、C_<60>の新しい機能としても注目に値する。一方、酸素、窒素や硫黄などのヘテロ原子を持つ超大環状化合物の合成にも成功し、これらの化合物をC_<60>と反応させることで、対応する土星型超分子錯体が生成していることをスペクトル的に確認することができた。さらに、合成に成功した超大環状化合物の金属イオンに対する包接能を検討した。特に、ある種の窒素原子を含む大環状化合物が特異的にアンチモン(V)イオンと錯形成する能力があることを見出した。

Research Products

(23 results)

All Other

All Publications (23 results)

[Publications] Yoshihiro Yamaguchi et al.: "Creation of Nanoscale Oxaarenecyclynes and Their C_<60> Complexes"Tetrahedron Lett.. 43. 3277-3280 (2002)
[Publications] Shigeya Kobayashi et al.: "Shape-Persistent Cyclyne-type Azamacrocycles : Synthesis, Unusual Light-Emitting Characteristics, and Specific Recognition of the Sb(V) Ion"Tetrahedron Lett.. 44. 1469-1472 (2003)
[Publications] Shigeya Kobayashi et al.: "Synthesis and Properties of Novel Thiaarenecyclynes"Tetrahedron Lett.. 44. 1807-1810 (2003)
[Publications] Takahiro Nishimura et al.: "Palladium-Catalyzed Asymmetric Arylation of tert-Cyclobutanols via Enantioselective C-C Bond Cleavage"Chem. Commun.. 44. 50-51 (2002)
[Publications] Takahiro Nishimuia et al.: "Palladium-Catalyzed Kinetic Resolution of tert-Cyclobutanols via C-C Bond Cleavagc"Tetrahedron Lett.. 43. 3037-3039 (2002)
[Publications] Yasumari Maeda et al.: "Oxovanadium Complex-Catalyzed Aerobic Oxidatioti of Propargyic Alcohols"J. Org. Chem.. 67. 6718-6724 (2002)
[Publications] Yoshihiro Miyake et al.: "Asymmetric Synthesis of Epoxides from Aromatic Aldehydes and Benzyl Halides Catalyzed by C_2 Symmetric Optically Active Sulfides Having Binaphthyl Skeleton"Heteroatom Chem.. 13. 270-275 (2002)
[Publications] Yoshihiro Miyake et al.: "Asymmetric Baeyer-Villiger Oxidation of Cyclic Ketones Using Chiral Organoselenium Catalysts"Bull. Chem. Soc. Jpn.. 75. 2233-2237 (2002)
[Publications] Tomochika Iwata et al.: "Pallaium(II) Complex-Catalysed Enantioselective Benzolylation of Alcohols Using Carbon Monoxide and Organobismuth(V) Compound"J. Chem Soc., Perkin Trans. 1. 1548-1554 (2002)
[Publications] Yoshihiro Miyake et al.: "Kinetic Resolution of Racemic Ferrocenylphosphine Compounds Using Optically Active Cyclic Selenoxides as Oxidants"Phosphorus, Sulfur, and Silicon. 177. 217-2108 (2002)
[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)
[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 (2003)
[Publications] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Cycloaddition of Propargylic Alcohols with Phenol Derivatives via Allenylidene Intermediates : Catalytic Use of the Allenylidene Ligand as C3 Unit"J. Am. Cham. Soc.. 124. 7900-7901 (2002)
[Publications] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Propargylation of Aromatic Compounds with Propargylic Alcohols"J. Am. Chem. Soc.. 124. 11846-11847 (2002)
[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)
[Publications] Yoshiaki Nishibayashi et al.: "Synthesis of Diruthenium m Complexes Containing Chiral Thiolate-Bridged Ligands and Their Application to Catalytic Propargylic Alkylation of Propargylic Alcohols with Acetone"Organometallics. 22. 873-876 (2003)
[Publications] Yoshiaki Nishibayashi et al.: "Propargylation of Aromatic Compounds with Propargylic Alcohols Catalyzed by Cationic Diruthenium Complex"Angew. Chme. Int. Ed.. 42(印刷中). (2003)
[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)
[Publications] Shin-ichi Takekuma et al.: "A Facile Preparation of 5-lsopropylidene-3,8-dimethyl-I(5H)-azulenone and its Crystal Structure"Bull. Chem. Soc. Jpn.. 75. 151-152 (2002)
[Publications] Shin-ichi Takekuma et al.: "An Efficient Preparation, the Structure and the Properties of I-Isopropyl-4-(3-guiaiazulenylmethylium)benzene Hexafluorophosphate and Tetra-fluoroborate"Tetrahedron Lett.. 43. 2073-2078 (2002)
[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)
[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)
[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)

2002 Fiscal Year Annual Research Report

バイキャップ型及び土星型フラーレン超分子錯体の創製と新機能開発

Principal Investigator

植村 榮 京都大学, 工学研究科, 教授 (70027069)

Research Products

[Publications] Yoshihiro Yamaguchi et al.: "Creation of Nanoscale Oxaarenecyclynes and Their C_<60> Complexes"Tetrahedron Lett.. 43. 3277-3280 (2002)

[Publications] Shigeya Kobayashi et al.: "Shape-Persistent Cyclyne-type Azamacrocycles : Synthesis, Unusual Light-Emitting Characteristics, and Specific Recognition of the Sb(V) Ion"Tetrahedron Lett.. 44. 1469-1472 (2003)

[Publications] Shigeya Kobayashi et al.: "Synthesis and Properties of Novel Thiaarenecyclynes"Tetrahedron Lett.. 44. 1807-1810 (2003)

[Publications] Takahiro Nishimura et al.: "Palladium-Catalyzed Asymmetric Arylation of tert-Cyclobutanols via Enantioselective C-C Bond Cleavage"Chem. Commun.. 44. 50-51 (2002)

[Publications] Takahiro Nishimuia et al.: "Palladium-Catalyzed Kinetic Resolution of tert-Cyclobutanols via C-C Bond Cleavagc"Tetrahedron Lett.. 43. 3037-3039 (2002)

[Publications] Yasumari Maeda et al.: "Oxovanadium Complex-Catalyzed Aerobic Oxidatioti of Propargyic Alcohols"J. Org. Chem.. 67. 6718-6724 (2002)

[Publications] Yoshihiro Miyake et al.: "Asymmetric Synthesis of Epoxides from Aromatic Aldehydes and Benzyl Halides Catalyzed by C_2 Symmetric Optically Active Sulfides Having Binaphthyl Skeleton"Heteroatom Chem.. 13. 270-275 (2002)

[Publications] Yoshihiro Miyake et al.: "Asymmetric Baeyer-Villiger Oxidation of Cyclic Ketones Using Chiral Organoselenium Catalysts"Bull. Chem. Soc. Jpn.. 75. 2233-2237 (2002)

[Publications] Tomochika Iwata et al.: "Pallaium(II) Complex-Catalysed Enantioselective Benzolylation of Alcohols Using Carbon Monoxide and Organobismuth(V) Compound"J. Chem Soc., Perkin Trans. 1. 1548-1554 (2002)

[Publications] Yoshihiro Miyake et al.: "Kinetic Resolution of Racemic Ferrocenylphosphine Compounds Using Optically Active Cyclic Selenoxides as Oxidants"Phosphorus, Sulfur, and Silicon. 177. 217-2108 (2002)

[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)

[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 (2003)

[Publications] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Cycloaddition of Propargylic Alcohols with Phenol Derivatives via Allenylidene Intermediates : Catalytic Use of the Allenylidene Ligand as C3 Unit"J. Am. Cham. Soc.. 124. 7900-7901 (2002)

[Publications] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Propargylation of Aromatic Compounds with Propargylic Alcohols"J. Am. Chem. Soc.. 124. 11846-11847 (2002)

[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)

[Publications] Yoshiaki Nishibayashi et al.: "Synthesis of Diruthenium m Complexes Containing Chiral Thiolate-Bridged Ligands and Their Application to Catalytic Propargylic Alkylation of Propargylic Alcohols with Acetone"Organometallics. 22. 873-876 (2003)

[Publications] Yoshiaki Nishibayashi et al.: "Propargylation of Aromatic Compounds with Propargylic Alcohols Catalyzed by Cationic Diruthenium Complex"Angew. Chme. Int. Ed.. 42(印刷中). (2003)

[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)

[Publications] Shin-ichi Takekuma et al.: "A Facile Preparation of 5-lsopropylidene-3,8-dimethyl-I(5H)-azulenone and its Crystal Structure"Bull. Chem. Soc. Jpn.. 75. 151-152 (2002)

[Publications] Shin-ichi Takekuma et al.: "An Efficient Preparation, the Structure and the Properties of I-Isopropyl-4-(3-guiaiazulenylmethylium)benzene Hexafluorophosphate and Tetra-fluoroborate"Tetrahedron Lett.. 43. 2073-2078 (2002)

[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)

[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)

[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)

植村榮京都大学, 工学研究科, 教授 (70027069)