The Development of New Radical Processes

该项目将探索几种合成潜力 重要的自由基过程：环丙基的断裂 和环丁基原基自由基;生成，反转和 二氧戊环基、环氧乙烷基和氮丙啶基自由基的环化。 这些后一种官能化的自由基可以由以下物质产生： 容易获得的手性前体， 对映体纯的化合物。 二氧戊环基，环氧乙烷基，和 氮丙啶基自由基还没有成为广泛的主题， 研究，在后两种情况下，所有，但忽视， 化学合成中潜在的手性反应物。 此外 这些过程的合成潜力， 也提出了机械问题。 的成功 这些研究将提供新的合成途径， 适用于重要抗生素的制备， 通过阴离子和阳离子方法不可接近的途径。 现代 化学分析方法，即，核磁共振 和质谱，将用于鉴定 在这项工作中准备的新材料。 %%% 有了这个奖项，有机合成计划将支持 弗雷德里克·E博士的研究耶鲁大学的齐格勒。 的 研究探索基于免费的新合成方法 基于自由基的反应，可以取代更好的 开发了基于阴离子和阳离子的方法。

This project will explore the synthetic potential of several important radical processes: the fragmentation of cyclopropyl and cyclobutylcarbinyl radicals; the generation, inversion and cyclization of dioxolanyl, oxiranyl, and aziridinyl radicals. These latter functionalized radicals can be generated from readily available chiral precursors that will lead to enantiomerically pure compounds. Dioxolanyl, oxiranyl, and aziridinyl radicals have not been the subject of extensive study and in the case of the latter two, all but ignored as potential chiral reactants in chemical synthesis. In addition to the synthetic potential of these processes, interesting mechanistic questions have also been posed. The success of these studies will provide new avenues of synthesis that may be applicable to the preparation of important antibiotics through pathways inaccessible by anionic and cationic methods. Modern methods of chemical analysis, i.e., nuclear magnetic resonance and mass spectroscopy, will be used in the identification of the new materials prepared in this work. %%% With this award, the Organic Synthesis Program will support the research of Dr. Frederick E. Ziegler at Yale University. The research explores new synthetic methodology based on free radical based reactions that could replace the more well developed anionic and cationic based methodology.