SILICON MEDIATED HOMOLOGATION REACTIONS

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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.