1990 Fiscal Year Final Research Report Summary
Ring Transformations of Small-Ring Compounds Utilizing Chemical Properties of Heteroatoms
| Project/Area Number |
01470089
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Osaka University |
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Principal Investigator |
OHSHIRO Yoshiki Osaka University, Faculty of Engineering, Professor, 工学部, 教授 (70028984)
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| Co-Investigator(Kenkyū-buntansha) |
HIRAO Toshikazu Osaka University, Faculty of Engineering, Assistant Professor, 工学部, 助手 (90116088)
KOMATSU Mitsuo Osaka University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (60029197)
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| Project Period (FY) |
1989 – 1990
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| Keywords | Heteroatom / Small Ring Compound / Ring Transformation / Cyclopropane / Three-Membered Ring / Ring Enlargement / Heterocyclic Compound / 環拡大付加 |
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| Research Abstract |
Purpose of this study is to develop novel ring transformations utilizing large ring strain of small ring compounds and chemical properties of heteroatoms in or adjacent to the rings. Among them, onlyfunctionalized cylopropanes and three-membered heterocycles were studied to clarify their natures and to apply them to new synthetic reactions.
1. Basic or acidic treatment of dibromocylopropane carboxylate afforded bromobutenolides.
2. Synthetic methods of dihalocyclopropyl isocyanates were established and basic treatment of a urea derivative gave an imidazolinone ring.
3. Highly effective carboxylation was performed by the reaction of 1-cyano-1-trimethylsilyl-cyclopropane with carbon dioxide under mild conditions, at room temperature and ambient pressure, in the presence of cesium fluoride as desilylating agent.
4. Formation of allene derivative from 1-bromo-1-trimethylsilylcyclopropane via an allyl cation intermediate was found upon treatment with silver tetrafluoroborate.
5. Ring enlargement of a diaziridinone to diazetidinones was successful in the reaction with acetylides.
6. Diaziridinone reacted with hydroxyketones to give 1:1 ring-opened adducts which gave nitrogen-containing medium-sized heterocycles when treated with an acid.
7. Functionalized pyrazolinones or novel spiro heterocycles were prepared by ring-expanding addition of diaziridinone with compounds having an active methylene.
8. Pyrrolotriazine derivatives were synthesized by the reaction of diaziridinones with pyrrole derivatives.
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