Minority Predoctoral Fellowship Program

描述（由申请人提供）：烯丙基硅烷作为碳-碳键形成转化的反应物在合成中是不可或缺的。桥头堡烯丙硅烷是这些重要中间体中最近发现但尚未研究的亚类。该建议包括研究桥头堡烯基硅烷碳-碳成键反应的大纲。这些化合物的新型立体电子环境将用于指导不对称反应中的亲电试剂。通过这些研究获得的机械知识将扩展到目前对烯丙基硅烷反应性的理解。此外，桥头堡烯丙硅烷在合成中的应用将在天然产物Upial的方法中进行演示。

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.