Exploration for Regioselective fullerene derivatives via of synthetic intermediates fulleroid/azafulleroid having high reactive anti-Bredt double bonds
| Project/Area Number |
24750039
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| Research Category |
Grant-in-Aid for Young Scientists (B)
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| Allocation Type | Multi-year Fund |
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| Research Field |
Organic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
NAOHIKO Ikuma 大阪大学, 工学(系)研究科(研究院), 助教 (70505990)
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| Research Collaborator |
OSHIMA Takumi 大阪大学, 工学研究科, 教授 (40107082)
KOKUBO Ken 大阪大学, 工学研究科, 講師 (20304008)
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| Project Period (FY) |
2012-04-01 – 2014-03-31
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| Project Status |
Completed (Fiscal Year 2013)
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| Budget Amount *help |
¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2013: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2012: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
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| Keywords | 構造有機化学 / フラーレン / 位置選択的反応 / anti-Bredt二重結合 / 酸化的脱アミノ化 / ambident反応性 / 反ブレッド則 / エナミン / ambident求核性 / 酸触媒芳香族化反応 / 酸触媒反応 / 酸化反応 / 反応機構解析 / 分子軌道計算 |
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| Research Abstract |
Electrophilic/acidic/nucleophilic additions to fulleroid/azafulleroid with anti-Bredt double bonds were investigated to evaluate their regioselectivity and discover novel reactions. Electrophilic oxidant mCPBA reacted with fulleroid to give hydroxyester products while oxidation with C60 gave epoxides. On the other hand, the oxidation with azafulleroid preferentially lead to the oxidation of nitrogen bridge, followed by oxidative deamination to give pristine C60. Acid catalytic arylation of azafulleroids lead to monoarylated/pentakisarylated products, depended on the ambident basicity of anti-Bredt enamine moiety of azafulleroids. Moreover, nucleophilic addition of Grignard reagents with azafulleroid gave highly regioselective adduct due to the nitrogen coordination with the magnesium.
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Report
(3 results)
Research Products
(57 results)
