2002 年度実績報告書

炭素クラスター複合体の精密有機合成化学

研究課題

研究課題/領域番号	13001002
研究機関	東京大学
研究代表者	中村栄一東京大学, 大学院・理学系研究科, 教授 (00134809)
研究分担者	赤阪健筑波大学, 化学系, 教授 (60089810) 澤村正也北海道大学, 大学院・理学研究科・化学系専攻, 教授 (40202105)
キーワード	フラーレン / 炭素クラスター / 有機合成化学 / バッキーフェロセン / シャトルコック液晶 / 有機銅試薬 / DNA / ベシクル
研究概要	新しい物質の大量供給を可能とすることで,医学,ナノテクノロジーなど広く物質科学分野に波及効果をもつ研究が展開しつつある.代表的な研究成果は以下のようなものである. 1)高効率多重付加反応の開拓:研究代表者の中村は,高効率・高選択的炭素クラスター化学修飾反応をさらに機能性分子合成に有効な手法とすべく研究を進め,有機銅試薬の多重付加反応が広範な官能基の導入に適したものであることを示した.研究分担者である赤阪はいまだ構造の定まらなかった高次金属内包フラーレンの完全構造決定に成功した.中村・赤阪は,高次金属内包フラーレンを基礎骨格とした有機物質の供給を可能とすべく,化学修飾金属内包フラーレンの創製に共同で取り組んでいる. 2)材料科学への展開:フラーレンシクロペンタジエンを基礎骨格として,機能性材料へ応用可能なさまざまな有機物質を創製した.フラーレン骨格から共役π電子系を「切り出す」ことにより最短ナノチューブの合成を行い,「球と羽根」の新しい形式での分子認識によるフラーレン液晶をつくりだすことに成功した.また,フェロセンとフラーレンが融合したバッキーフェロセンの合成に成功した. 3)生物学への展開:独自に見いだしたフラーレン-アミン複合体による遺伝子導入手法をさらに深化させるべく研究を進め,フラーレンがDNA単分子の凝縮剤として作用することを見いだした.

研究成果

(20件)

すべてその他

すべて文献書誌 (20件)

[文献書誌] 澤村正也: "Regioselective Penta-addition of 1-Alkenyl Copper Reagent to [60]Fullerene. Synthesis of Penta-alkenyl FCp Ligand"Journal of the Organometallic Chemistry. 652. 31-35 (2002)
[文献書誌] 中村正治: "Carbozincation of Dipolar Trimethylenemethane. A New Route to Functionalized Organozinc Reagents"Chemistry Letters. 146-147 (2002)
[文献書誌] 磯部寛之: "Synthesis of Disubstituted Cucurbit[6]uril and Its Rotaxane Derivative"Organic Letters. 4. 1287-1289 (2002)
[文献書誌] 中村栄一: "Mechanism of C-H Bond Activation/C-C Bond Formation Reaction between Diazo Compound and Alkane Catalyzed by Dirhodium Tetracarboxylate"Journal of the American Chemical Society. 124. 7181-7192 (2002)
[文献書誌] 澤村正也: "Cu(I)-Mediated Regioselective Tri-addition of Grignard Reagent to [70]Fullerene. Synthesis of Indenyl-type Metal Ligand Embedded into Graphitic Structure"Journal of Materials Chemistry. 12. 2109-2115 (2002)
[文献書誌] 澤村正也: "Hybrid of Ferrocene and Fullerene"Journal of the American Chemical Society. 124. 9354-9355 (2002)
[文献書誌] 山中正浩: "Density Functional Studies on Kinetic Reactivity of "Higher Order"Lipshutz Cuprate in Addition Reaction to Acetylene"Bulletin of the Chemical Society Japan. 75. 1815-1818 (2002)
[文献書誌] 澤村正也: "Stacking of conical molecules with a fullerene apex into polar columns in crystals and liquid crystals"Nature. 419. 702-705 (2002)
[文献書誌] 中村正治: "Reaction Pathways of the Simmons-Smith Reaction"Journal of the American Chemical Society. 125. 2341-2350 (2003)
[文献書誌] 中村栄一: "Synthesis, Structure and Aromaticity of a Hoop-shaped Cyclic Benzenoid [10]Cyclophenacene"Journal of the American Chemical Society. 125. 2834-2835 (2003)
[文献書誌] 藤井彰彦: "Photocurrent Enhancement in Conducting Polymer Device by Doping with Endohedral Metallofullerene La@C_<82>"Japan Journal of Applied Physics. 41. 2254-2255 (2002)
[文献書誌] 高口豊: "Reversible C_<60> Binding to Anthracene-Having Dendritic Poly(amide amine)Substituent Producing an Acidic Water-soluble Fullerodendrimer"Angewante Chemie International Eddition. 41. 817-819 (2002)
[文献書誌] Y.Niino: "Photochemical Decomposition of Pyrazoline Produced in the Reaction of C_<60> with Diazoadamantane"ITE Letters. 3. C60-C63 (2002)
[文献書誌] 中島直敏: "Construction of a Metallofullerene La@C_<82>/Artificial Lipid Film-Modified Electrode Device and Its Electron Transfer"Journal of Physical Chemistry B. 106. 3523-3525 (2002)
[文献書誌] 若原孝次: "Silylation of Higher Fullerenes"Journal of Materials Chemical. 12. 2061-2064 (2002)
[文献書誌] 若原孝次: "Ionization and Structural Determination of the Major Isomer of Pr@C_<82>"Chemical Physics Letters. 360. 235-239 (2002)
[文献書誌] 若原孝次: "A Non-spectroscopic Method to Determine the Photolytic Decomposition Pathways of 3 Chloro-3-alkyldiazirine ; Carbene, Diazo and Rearrangement in Excited State"Journal of the American Society. 124. 9465-9468 (2002)
[文献書誌] 中村栄一(分担), Manfred Schlosser編: "Organometallic Chemistry, Method, 2^<nd> edition"Wiley. (2002)
[文献書誌] 中村栄一(分担), Nobert Krause Ed編: "Organocopper Chemistry"Wiley-VCH. (2002)
[文献書誌] 中村栄一(分担), 有機合成化学協会編: "有機合成創造の軌跡(My Favorite Organic Synthesis)"化学同人. (2002)

2002 年度 実績報告書

炭素クラスター複合体の精密有機合成化学

研究代表者

中村 栄一 東京大学, 大学院・理学系研究科, 教授 (00134809)

研究成果

[文献書誌] 澤村正也: "Regioselective Penta-addition of 1-Alkenyl Copper Reagent to [60]Fullerene. Synthesis of Penta-alkenyl FCp Ligand"Journal of the Organometallic Chemistry. 652. 31-35 (2002)

[文献書誌] 中村正治: "Carbozincation of Dipolar Trimethylenemethane. A New Route to Functionalized Organozinc Reagents"Chemistry Letters. 146-147 (2002)

[文献書誌] 磯部寛之: "Synthesis of Disubstituted Cucurbit[6]uril and Its Rotaxane Derivative"Organic Letters. 4. 1287-1289 (2002)

[文献書誌] 中村栄一: "Mechanism of C-H Bond Activation/C-C Bond Formation Reaction between Diazo Compound and Alkane Catalyzed by Dirhodium Tetracarboxylate"Journal of the American Chemical Society. 124. 7181-7192 (2002)

[文献書誌] 澤村正也: "Cu(I)-Mediated Regioselective Tri-addition of Grignard Reagent to [70]Fullerene. Synthesis of Indenyl-type Metal Ligand Embedded into Graphitic Structure"Journal of Materials Chemistry. 12. 2109-2115 (2002)

[文献書誌] 澤村正也: "Hybrid of Ferrocene and Fullerene"Journal of the American Chemical Society. 124. 9354-9355 (2002)

[文献書誌] 山中正浩: "Density Functional Studies on Kinetic Reactivity of "Higher Order"Lipshutz Cuprate in Addition Reaction to Acetylene"Bulletin of the Chemical Society Japan. 75. 1815-1818 (2002)

[文献書誌] 澤村正也: "Stacking of conical molecules with a fullerene apex into polar columns in crystals and liquid crystals"Nature. 419. 702-705 (2002)

[文献書誌] 中村正治: "Reaction Pathways of the Simmons-Smith Reaction"Journal of the American Chemical Society. 125. 2341-2350 (2003)

[文献書誌] 中村栄一: "Synthesis, Structure and Aromaticity of a Hoop-shaped Cyclic Benzenoid [10]Cyclophenacene"Journal of the American Chemical Society. 125. 2834-2835 (2003)

[文献書誌] 藤井彰彦: "Photocurrent Enhancement in Conducting Polymer Device by Doping with Endohedral Metallofullerene La@C_<82>"Japan Journal of Applied Physics. 41. 2254-2255 (2002)

[文献書誌] 高口 豊: "Reversible C_<60> Binding to Anthracene-Having Dendritic Poly(amide amine)Substituent Producing an Acidic Water-soluble Fullerodendrimer"Angewante Chemie International Eddition. 41. 817-819 (2002)

[文献書誌] Y.Niino: "Photochemical Decomposition of Pyrazoline Produced in the Reaction of C_<60> with Diazoadamantane"ITE Letters. 3. C60-C63 (2002)

[文献書誌] 中島直敏: "Construction of a Metallofullerene La@C_<82>/Artificial Lipid Film-Modified Electrode Device and Its Electron Transfer"Journal of Physical Chemistry B. 106. 3523-3525 (2002)

[文献書誌] 若原孝次: "Silylation of Higher Fullerenes"Journal of Materials Chemical. 12. 2061-2064 (2002)

[文献書誌] 若原孝次: "Ionization and Structural Determination of the Major Isomer of Pr@C_<82>"Chemical Physics Letters. 360. 235-239 (2002)

[文献書誌] 若原孝次: "A Non-spectroscopic Method to Determine the Photolytic Decomposition Pathways of 3 Chloro-3-alkyldiazirine ; Carbene, Diazo and Rearrangement in Excited State"Journal of the American Society. 124. 9465-9468 (2002)

[文献書誌] 中村栄一(分担), Manfred Schlosser編: "Organometallic Chemistry, Method, 2^<nd> edition"Wiley. (2002)

[文献書誌] 中村栄一(分担), Nobert Krause Ed編: "Organocopper Chemistry"Wiley-VCH. (2002)

[文献書誌] 中村栄一(分担), 有機合成化学協会編: "有機合成 創造の軌跡(My Favorite Organic Synthesis)"化学同人. (2002)

2002 年度実績報告書

中村栄一東京大学, 大学院・理学系研究科, 教授 (00134809)

[文献書誌] 高口豊: "Reversible C_<60> Binding to Anthracene-Having Dendritic Poly(amide amine)Substituent Producing an Acidic Water-soluble Fullerodendrimer"Angewante Chemie International Eddition. 41. 817-819 (2002)

[文献書誌] 中村栄一(分担), 有機合成化学協会編: "有機合成創造の軌跡(My Favorite Organic Synthesis)"化学同人. (2002)