Studies in Ring Expansion

The work described in this thesis has been divided into three parts: Chapter One describes several unsuccessful attempts to add dichlorocarbene to the enol-acetate derived from bicyclo [3.3.1.] nonan-9-one. This was intended as a new route to the relatively inaccessible bicyclo[4.3.1.] deca-2,10-dione system. Chapter Two is concerned with investigations into the fragmentations of 4-tosyloxy bicyclo [3.2.1.] and [3.3.1.] alkanones as routes into specifically-substituted medium ring compounds. Two new fragmentation reactions are described, one of which has been studied in detail. Also included is a discussion of the ractors affecting the hydrolysis of certain cycloheptene gem-diesters. Chapter Three outlines synthetic approaches to a possible intermediate in the biogenesis of sesquiterpenes of the carotane family. No sesquiterpene as such has been isolated, but it is believed that with suitable modification of the reaction conditions, such a synthesis might have been achieved