Abstract
Abstract The studies described in this thesis are divided into two parts : 1. Studies on the facial selectivity in the addition of vinylmagnesium bromide to bicyclo[2.2.2]oct-5-en-2ones, and 2. Studies in the structural variations for [1,3]sigmatropic rearrangement of 4-oxatricyclo[4.3.1.03,7]dec-8-en-2-ols 51. In the first part, addition of vinylmagnesium bromide to bicyclo [2.2.2]oct-5-en-2-one derivatives 52 and 55 gave the diastereo-selective alcohols. And synthesis of 4-oxatricyclo[4.3.1.03,7]dec-8-en-2-ones 55, selectivity control to produce the desired syn or anti diastereomer was achieved by manipulating the reaction conditions. When use Lewis acid as catalysis, we will get high selectivity anti addition product; use the vinylmagnesium bromide and CeCl3 complex as addition reagent, we will get high selectivity syn addition product. If use the bicyclo[2.2.2]oct-5-en-2-ol as the starting material, we will selectivity get syn addition product. The second part deals with the studies on the structural variations for [1,3]sigmatropic rearrangement of 4-oxatricyclo[4.3.1.03,7]dec-8-en-2-ols 51 and bicyclo[2.2.2]oct-5-en-2-ols 50. Our results indicate the structural requirements for the bicyclo[2.2.2]oct-5-en-2-ols derivatives to undergo [1,3]sigmatropic rearrangement. It is only the compound that have ketal, ether ring, tricyclo and 4-oxa fragment 53 will undergo [1,3]sigmatropic rearrangement.