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

γ-环糊精双帽C60超分子复合物和C60超大杂环新分子功能的开发

• 批准号: 13305062
• 负责人: UEMURA Sakae
• 金额: $ 35.28万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13305062/
• 关键词: fullerene; cyclodextrin; large-membered ring compound; asymmetric reduction; nitrogen fixation; ammonia; heteroatom; inclusion compound; 不斉還元反応; ケトン; アルコール

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.

自从<60>基于超芳香性理论首次预言了足球结构的C_（buckminsterfullerence）分子的存在以来，人们对C_（buckminsterfullerence）及其衍生物的反应性和功能产生了浓厚的兴趣<60>。本文设计并成功地制备了水溶性的C_<60>（10）/γ-环糊精（1：2）包合物（γ-环糊精-双帽C_<60><60>（10））。在我们的研究过程中，我们发现了γ-环糊精双帽C_2在不<60>对称还原烯酮和N_2固氮成氨中的新功能.γ-环糊精双帽C_2<60>以NaBH_4为还原剂，介导前手性烷基芳基酮的不对称还原，得到相应的手性仲醇，具有中等的对映选择性. γ-环糊精双帽C_2<60>与过量的连二亚硫酸钠在1个N_2原子下于60 ℃反应1h，得到中等产率的氨.我们认为，<60>在γ-环糊精双帽C_2中，C_2分子表面的配位N_2<60>转化为氨。在相似的反应条件下，用稀硫酸也可得到较低产率的氨。在这两种情况下，在没有N_2或γ-环糊精-双帽C_2存在下，均未观察到氨的形成<60>。这一显著的结果可能是第一个只用碳、氢、氧元素将N_2气转化为氨的例子。

项目成果

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)

Yoshihiro Miyake 等人：“使用 CO 和有机铋 (V) 化合物通过手性 Pd(II) 复合物催化的对映选择性苯甲酰化反应动力学拆分仲醇”Chem.Commun. 2584-2585 (2001)

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)

Yoshiaki Nishibayashi 等人：“钌催化的丙炔醇与酮的丙炔烷基化：γ-酮乙炔的直接合成”J.Am.Chem.Soc.. 123. 3393-3394 (2001)

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)

Toshiyuki Ohe 等人：“使用芳基锡和四芳基硼酸钠的钯 (II) 催化的硝基烯烃的迈克尔型氢芳基化”Bull.Chem.Soc.Jpn.. 76（出版中）。

Yasunari Maeda et al.: "Oxovanadium Complex-Catalyzed Oxidation of Propargylic Alcohols Using Mojecular Oxygen"Tetrahedron Lett.. 42. 8877-8879 (2001)

Yasunari Maeda 等人：“氧钒复合物-利用分子氧催化炔丙醇的氧化”Tetrahedron Lett.. 42. 8877-8879 (2001)

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)

Yoshihiro Miyake等人：“由具有联萘骨架的0pically活性硫化物催化的芳香醛和卤化苄的环氧化物的不对称合成”Heteroatont Chem.. 13. 270-275 (2002)