2003 Fiscal Year Annual Research Report

炭素クラスター複合体の精密有機合成化学

Research Project

Project/Area Number	13001002
Research Institution	The University of Tokyo
Principal Investigator	中村栄一東京大学, 大学院・理学研究科, 教授 (00134809)
Co-Investigator(Kenkyū-buntansha)	赤阪健筑波大学, 化学系, 教授 (60089810) 松尾豊東京大学, 大学院・理学研究科, 助手 (00334243)
Keywords	フラーレン / 炭素クラスター / DNA / 遺伝子導入 / ベシクル / 液晶 / ポリアセン / 錯体触媒
Research Abstract	本特別推進研究では,実験および理論化学的手法を駆使して「感銘直截・高効率・高選択的」な究極的有機合成を炭素クラスターの世界に実現し,これによって次世代の材料科学,ナノテクノロジーや医学に資する新しい物質科学を創成することを目的として研究を行っている。本年度は,これまでに確立した炭素クラスターの化学修飾反応の適用範囲を拡大すると同時に,最適化した化学修飾反応を鍵として炭素クラスターを基にした機能分子の設計・合成を引き続き行った。例えば,フテーレンへ10個の有機基を導入することにより,これまで合成が達成されていなかった環状共役系「[10]シクロフェナセン」の合成を行い,その構造や化学的に安定な性質,そして,電気化学的性質や光化学的性質を明らかにした。また,水中でフラーレンに無保護糖を5つ導入する方法も開発した。さらに,球状のフラーレンにコーン状またはカップ状の部位を取り付け,球とコーンおよびカップの分子認識による分子集合体の構築を行い,その液晶などの機能性を明らかにした。赤阪は,金属内包フラーレンの化学修飾反応にも取り組み,閉殻の金属内包フラーレンイオン種を合成する方法を確立し,それらの熱安定性,光安定性を解明した。分担者の松尾は中村と協力して有機金属化学,触媒化学方面への展開を行い,フラーレンの光や電子に対する刺激応答性を利用した新しい触媒になることが期待される種々のフラーレン-遷移金属錯体を合成した。

Research Products

(19 results)

All Other

All Publications (19 results)

[Publications] Masahiro Yamanaka: "Theoretical Studies on Structures and Reactivities of Organocuprate(I) and Organocopper(III) Species"Journal of Computational Chemistry. 24. 1401-1409 (2003)
[Publications] Masaharu Nakamura: "Reaction Pathways of the Simmons-Smith Reaction"Journal of the American Chemical Society. 125. 2341-2350 (2003)
[Publications] Eiichi Nakamura: "Synthesis, Structure, and Aromaticity of a Hoop-Shaped Cyclic Benzenoid [10] Cyclophenacene"Journal of the American Chemical Society. 125. 2834-2835 (2003)
[Publications] Yutaka Matsuo: "Ruthenium (II) Complexes of Pentamethylated [60]Fullerene Alkyl, Alkynyl, Chloro, Isocyanide, Phosphine Complexes"Organometallics. 22. 2554-2563 (2003)
[Publications] Masaharu Nakamura: "Iron-Catalyzed Regio-and Stereoselective Ring Opening of [2.2.1]- and [3.2.1]Oxabicyclic Alkenes with a Grignard Reagent"Organic Letters. 5. 1373-1375 (2003)
[Publications] Masaharu Nakamura: "Enantioselective Synthesis of Alpha-Substituted Ketones by Asymmetric Addition of Chiral Zinc Enamides to 1-Alkenes"Journal of the American Chemical Society. 125. 6362-6363 (2003)
[Publications] Motoki Toganoh: "Regioselective Synthesis of [60]Fullerene η^5-Indenide R_3C_<60>^- and η^5-Cyclopentadienide R_5C_<60>^-Bearing Different R Groups"Organic & Biomolecular Chemistry. 1. 2604-2611 (2003)
[Publications] Tomoki Shirakawa: "Doping Effects of Novel Fullerene Derivatives in Conducting Polymer"Synthetic Metals. 137. 1415-1416 (2003)
[Publications] Motoki Toganoh: "Rhenium-templated Regioselective Polyhydrogenation of [60]Fullerene and Derivatives. Rhenium η^5-Complexes of Hydrofullerenes"Angewandte Chemie International Edition. 42. 3530-3532 (2003)
[Publications] Yutaka Matsuo: "Theoretical Studies on Structures and Reactivities of Finite-Length Single Wall Armchair Carbon Nanotubes"Organic Letters. 5. 3181-3184 (2003)
[Publications] Naohiko Yoshikai: "Theoretical Studies on Diastereo- and Enantioselective Rhodium-Catalyzed Cyclization of Diazo Compound via Intramolecular C-H Bond Insertion"Advanced Synthesis and Catalysis. 345. 1139-1145 (2003)
[Publications] Masaharu Nakamura: "Indium-Catalyzed Addition of Active Methylene Compounds to 1-Alkynes"Journal of the American Chemical Society. 125. 13002-13003 (2003)
[Publications] Hiroyuki Isobe: "Synthesis of Fullerene Glycoconjugates through Sulfide Connection in Aqueous Media"Organic Letters. 5. 4461-4463 (2003)
[Publications] Motoki Toganoh: "Synthesis and Catalytic Activity of Rhodium Diene Complexes Bearing Indenyl-Type Fullerene η^5-Ligand"Journal of Organometallic Chemistry. 683. 295-300 (2003)
[Publications] Motoki Toganoh: "Synthesis of Ferrocene/Hydrofullerene Hybrid and Functionalized Bucky Ferrocenes"Journal of the American Chemical Society. 125. 13974-13975 (2003)
[Publications] Yutaka Matsuo: "Synthesis and Reactivity of Bucky Ruthenocene Ru(η^5-C_<60>Me_5)(η^5-C_5H_5)"Chemistry Letters. 33. 68-69 (2004)
[Publications] Yutaka Matsuo: "Stacking of Molecules Possessing a Fullerene Apex and a Cup-shaped Cavity Connected by Silicon-Connection"Journal of the American Chemical Society. 126. 432-433 (2004)
[Publications] Ryo Hamasaki: "Synthesis of Functionalized Fullerene by Mono-alkylation of Fullerene Cyclopentadienide"Chemistry Letters. 33. 328-329 (2004)
[Publications] 中村栄一, 松尾豊(Chapter2-1執筆): "有機金属反応剤ハンドブック(玉尾皓平編)"化学同人. 260 (2003)

2003 Fiscal Year Annual Research Report

炭素クラスター複合体の精密有機合成化学

Principal Investigator

中村 栄一 東京大学, 大学院・理学研究科, 教授 (00134809)

Research Products

[Publications] Masahiro Yamanaka: "Theoretical Studies on Structures and Reactivities of Organocuprate(I) and Organocopper(III) Species"Journal of Computational Chemistry. 24. 1401-1409 (2003)

[Publications] Masaharu Nakamura: "Reaction Pathways of the Simmons-Smith Reaction"Journal of the American Chemical Society. 125. 2341-2350 (2003)

[Publications] Eiichi Nakamura: "Synthesis, Structure, and Aromaticity of a Hoop-Shaped Cyclic Benzenoid [10] Cyclophenacene"Journal of the American Chemical Society. 125. 2834-2835 (2003)

[Publications] Yutaka Matsuo: "Ruthenium (II) Complexes of Pentamethylated [60]Fullerene Alkyl, Alkynyl, Chloro, Isocyanide, Phosphine Complexes"Organometallics. 22. 2554-2563 (2003)

[Publications] Masaharu Nakamura: "Iron-Catalyzed Regio-and Stereoselective Ring Opening of [2.2.1]- and [3.2.1]Oxabicyclic Alkenes with a Grignard Reagent"Organic Letters. 5. 1373-1375 (2003)

[Publications] Masaharu Nakamura: "Enantioselective Synthesis of Alpha-Substituted Ketones by Asymmetric Addition of Chiral Zinc Enamides to 1-Alkenes"Journal of the American Chemical Society. 125. 6362-6363 (2003)

[Publications] Motoki Toganoh: "Regioselective Synthesis of [60]Fullerene η^5-Indenide R_3C_<60>^- and η^5-Cyclopentadienide R_5C_<60>^-Bearing Different R Groups"Organic & Biomolecular Chemistry. 1. 2604-2611 (2003)

[Publications] Tomoki Shirakawa: "Doping Effects of Novel Fullerene Derivatives in Conducting Polymer"Synthetic Metals. 137. 1415-1416 (2003)

[Publications] Motoki Toganoh: "Rhenium-templated Regioselective Polyhydrogenation of [60]Fullerene and Derivatives. Rhenium η^5-Complexes of Hydrofullerenes"Angewandte Chemie International Edition. 42. 3530-3532 (2003)

[Publications] Yutaka Matsuo: "Theoretical Studies on Structures and Reactivities of Finite-Length Single Wall Armchair Carbon Nanotubes"Organic Letters. 5. 3181-3184 (2003)

[Publications] Naohiko Yoshikai: "Theoretical Studies on Diastereo- and Enantioselective Rhodium-Catalyzed Cyclization of Diazo Compound via Intramolecular C-H Bond Insertion"Advanced Synthesis and Catalysis. 345. 1139-1145 (2003)

[Publications] Masaharu Nakamura: "Indium-Catalyzed Addition of Active Methylene Compounds to 1-Alkynes"Journal of the American Chemical Society. 125. 13002-13003 (2003)

[Publications] Hiroyuki Isobe: "Synthesis of Fullerene Glycoconjugates through Sulfide Connection in Aqueous Media"Organic Letters. 5. 4461-4463 (2003)

[Publications] Motoki Toganoh: "Synthesis and Catalytic Activity of Rhodium Diene Complexes Bearing Indenyl-Type Fullerene η^5-Ligand"Journal of Organometallic Chemistry. 683. 295-300 (2003)

[Publications] Motoki Toganoh: "Synthesis of Ferrocene/Hydrofullerene Hybrid and Functionalized Bucky Ferrocenes"Journal of the American Chemical Society. 125. 13974-13975 (2003)

[Publications] Yutaka Matsuo: "Synthesis and Reactivity of Bucky Ruthenocene Ru(η^5-C_<60>Me_5)(η^5-C_5H_5)"Chemistry Letters. 33. 68-69 (2004)

[Publications] Yutaka Matsuo: "Stacking of Molecules Possessing a Fullerene Apex and a Cup-shaped Cavity Connected by Silicon-Connection"Journal of the American Chemical Society. 126. 432-433 (2004)

[Publications] Ryo Hamasaki: "Synthesis of Functionalized Fullerene by Mono-alkylation of Fullerene Cyclopentadienide"Chemistry Letters. 33. 328-329 (2004)

[Publications] 中村栄一, 松尾豊(Chapter2-1執筆): "有機金属反応剤ハンドブック(玉尾皓平編)"化学同人. 260 (2003)

中村栄一東京大学, 大学院・理学研究科, 教授 (00134809)