Ring Transformations of Small-Ring Compounds Utilizing Chemical Properties of Heteroatoms

本研究的目的是利用小环化合物的大环应变和环中或邻近环的杂原子的化学性质来开发新的环转换。其中，仅官能化的环丙烷和三元杂环化合物的研究旨在阐明其性质并将其应用于新的合成反应中.二溴环丙烷羧酸酯经碱或酸处理后得到溴代丁烯内酯.建立了二卤代环丙基异氰酸酯的合成方法，通过脲衍生物的碱性处理得到咪唑啉酮环. 1-氰基-1-三甲基硅基环丙烷与二氧化碳在温和条件下，以氟化铯为脱硅剂，在室温和常压下进行了高效的羧化反应.发现在用四氟硼酸银处理后，1-溴-1-三甲基硅基环丙烷通过烯丙基阳离子中间体形成丙二烯衍生物。在与乙炔基的反应中，成功地将二氮杂环丙啶酮扩环为二氮杂环丁烷酮.二氮丙啶酮与羟基酮反应生成1：1的开环加合物，加合物经酸处理后生成中等大小的含氮杂环化合物.通过二氮杂环丙啶酮与具有活性亚甲基的化合物的扩环加成，制备了官能化的吡唑啉酮或新型螺杂环。通过二氮杂环丙烷酮与吡咯衍生物反应，合成了吡咯并三嗪衍生物。

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.