| Project/Area Number |
11450348
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| Research Category |
Grant-in-Aid for Scientific Research (B).
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
KOMATSU Mitsuo Graduate School of Engineering Osaka University, Professor, 大学院・工学研究科, 教授 (60029197)
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| Co-Investigator(Kenkyū-buntansha) |
MINAKATA Satoshi Graduate School of Eng Osaka University, Lecturer, 大学院・工学研究科, 講師 (90273599)
柳 日馨 大阪大学, 大学院・工学研究科, 助教授 (80210821)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥14,500,000 (Direct Cost: ¥14,500,000)
Fiscal Year 2000: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 1999: ¥11,700,000 (Direct Cost: ¥11,700,000)
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| Keywords | Molecular nitrogen / Gaseous ammonia / Heterocycle synthesis / Nitrido complex / Chloramine-T / Aziridine / Pyrrolidine / N1 unit transfer reaction / 複素還合成 |
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| Research Abstract |
Syntheses of nitrogen-containing heterocycles were developed by using a nitrido complex and Chloramine-T, which can be prepared from molecular nitrogen and gaseous ammonia, respectively.
1. N1 unit transfer reaction using a nitrido complex
A nitridomanganese complex was found to be a good nitrogen source for aziridination of styrene derivatives and conjugated dienes with p-toluenesulfonic anhydride as an activating agent. When an acid chloride as an activator of the complex was applied to the reaction in the presence of a silver salt, oxazolines were obtained in good yields. Asymmetric version of these reactions could be achieved by using chiral nitridomanganese complexes.
2. N1 unit transfer reaction using Chloramine-T
i) The iodine-catalyzed aziridination of alkenes with Chloramine-T was applied to the selective synthesis of aziridines or pyrrolidine derivatives from alkenes having an iodo group at the γ-position by changing reaction conditions. ii) The iodine-catalyzed aziridination proceeded efficiently in an aqueous solution under phase transfer catalytic conditions. iii) Chloramine-T-silver salt system realized the aziridination of electron deficient alkenes, such as α, β-unsaturated ketones or esters. The system was successfully applied to the synthesis of nitrogen-containing bicyclic heterocycles from unconjugated dienes.
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