2002 年度実績報告書

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

研究課題

研究課題/領域番号	13305062
研究機関	京都大学
研究代表者	植村榮京都大学, 工学研究科, 教授 (70027069)
研究分担者	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)
キーワード	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
研究概要	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。

研究成果

(23件)

すべてその他

すべて文献書誌 (23件)

[文献書誌] Yoshihiro Yamaguchi et al.: "Creation of Nanoscale Oxaarenecyclynes and Their C_<60> Complexes"Tetrahedron Lett.. 43. 3277-3280 (2002)
[文献書誌] 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)
[文献書誌] Shigeya Kobayashi et al.: "Synthesis and Properties of Novel Thiaarenecyclynes"Tetrahedron Lett.. 44. 1807-1810 (2003)
[文献書誌] Takahiro Nishimura et al.: "Palladium-Catalyzed Asymmetric Arylation of tert-Cyclobutanols via Enantioselective C-C Bond Cleavage"Chem. Commun.. 44. 50-51 (2002)
[文献書誌] Takahiro Nishimuia et al.: "Palladium-Catalyzed Kinetic Resolution of tert-Cyclobutanols via C-C Bond Cleavagc"Tetrahedron Lett.. 43. 3037-3039 (2002)
[文献書誌] Yasumari Maeda et al.: "Oxovanadium Complex-Catalyzed Aerobic Oxidatioti of Propargyic Alcohols"J. Org. Chem.. 67. 6718-6724 (2002)
[文献書誌] 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)
[文献書誌] Yoshihiro Miyake et al.: "Asymmetric Baeyer-Villiger Oxidation of Cyclic Ketones Using Chiral Organoselenium Catalysts"Bull. Chem. Soc. Jpn.. 75. 2233-2237 (2002)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] Yoshiaki Nishibayashi et al.: "Ruthenium-Catalyzed Propargylation of Aromatic Compounds with Propargylic Alcohols"J. Am. Chem. Soc.. 124. 11846-11847 (2002)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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 年度 実績報告書

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

研究代表者

植村 榮 京都大学, 工学研究科, 教授 (70027069)

研究成果

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

[文献書誌] 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)

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

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

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

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

[文献書誌] 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)

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

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

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

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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 年度実績報告書

植村榮京都大学, 工学研究科, 教授 (70027069)