Minority Predoctoral Fellowship Program

描述(申请人提供)：烯丙基硅烷在合成中已成为碳-碳键形成转化中不可或缺的反应物。桥头烯丙基硅烷是这些重要中间体的一个新的但未被研究的亚类。该提案包括研究桥头烯丙基硅烷的碳-碳键形成反应的大纲。这些化合物的新型立体电子环境将被用来指导不对称反应中的亲电性。通过这些研究获得的机理知识将在目前对烯丙基硅烷反应性的理解基础上得到扩展。此外，桥头烯丙基硅烷在合成中的用途将在天然产物Upial的方法中继续进行。

DESCRIPTION (provided by applicant): Allylsilanes have become indispensable in synthesis as reactants in carbon-carbon bond forming transformations. Bridgehead allylsilanes are a recent but un-studied sub-class of these important intermediates. The proposal includes an outline for investigating the carbon-carbon bond forming reactions of bridgehead allylsilanes. The novel stereoelectronic environment of these compounds will be utilized to direct electrophiles in asymmetric reactions. The mechanistic knowledge gained through these investigations will expand upon current understanding of allylsilane reactivity. Additionally, a demonstration of the utility of bridgehead allylsilanes in synthesis will be pursued in an approach to the natural product, Upial.