| Project/Area Number |
13305062
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
有機工業化学
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
UEMURA Sakae Faculty of Engineering, Professor, 工学研究科, 教授 (70027069)
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| Co-Investigator(Kenkyū-buntansha) |
TAKEKUMA Shin-ichi Kinki University, Associate Professor, 理工学部, 助教授 (00171629)
NISHIMURA Takahiro Faculty of Engineering, Research Associate, 工学研究科, 助手 (50335197)
NISHIBAYASHI Yoshiaki Faculty of Engineering, Research Associate, 工学研究科, 助手 (40282579)
YAMAGUCHI Yoshihiro Kinki University, Lecturer, 理工学部, 講師 (30200637)
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| Project Period (FY) |
2001 – 2002
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| Project Status |
Completed (Fiscal Year 2002)
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| Budget Amount *help |
¥55,120,000 (Direct Cost: ¥42,400,000、Indirect Cost: ¥12,720,000)
Fiscal Year 2002: ¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000)
Fiscal Year 2001: ¥37,830,000 (Direct Cost: ¥29,100,000、Indirect Cost: ¥8,730,000)
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| Keywords | 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 |
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| Research Abstract |
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.
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