SILICON MEDIATED HOMOLOGATION REACTIONS

本研究的目的是探索一个 一组反应的具体建设的C-C键在灵活的或 非循环系统 这些反应涉及克莱森，卡罗尔， 和（2，3）-σ迁移重排和Peterson烯化反应 中间体烯丙基硅烷。 键结构和立体定向性是 维持和扩展，以提供对1-2，1-3，1-4， 1-5相对不对称中心 制备官能化的烯丙基硅烷， 其也允许新的成环反应。 虽然主要 我们的目标是尽我们所能地了解这些反应， 而不是追求全合成，反应将在 当前的合成问题如Prelog-Djerassi内酯的背景， 硼霉素，植醇，维生素D，以及生物碱和萜烯。

The goal of this research is to explore the scope and stereochemistry of a set of reactions for the specific construction of C--C bonds in flexible or acyclic systems. These reactions involve homologation of Claisen, Carroll, and (2,3)-sigmatropic rearrangements and the Peterson olefination via intermedate allylsilanes. The bond construction and stereospecificity is maintained and extended so as to provide control over 1-2, 1-3, 1-4, and 1-5 relative asymmetric centers. Functionalized allylsilanes are produced which allow novel ring-forming reactions as well. Although the primary goal is to learn all that we can about the reactions in question, rather than to pursue total synthesis, the reactions will be investigated in the context of current synthetic problems such as the Prelog-Djerassi lactone, Boromycin, Phytol, Vitamin D, as well as alkaloids and terpenes.