Minority Predoctoral Fellowship Program

描述（由申请人提供）：烯丙基硅烷在合成中作为碳-碳键形成转化的反应物已变得不可或缺。桥头烯丙基硅烷是这些重要中间体的一个最近但未研究的子类。该建议包括一个大纲，调查的碳-碳键形成反应的桥头烯丙基硅烷。这些化合物的新颖的立体电子环境将被用来指导亲电试剂的不对称反应。通过这些调查获得的机理知识将扩大目前的理解烯丙基硅烷的反应性。此外，桥头烯丙基硅烷在合成中的效用的演示将在天然产物Upial的方法中进行。

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.