Studies for the strategy and development of methodology toward the total synthesis of Daphnicyclidin d and Peloruside a.

摘要

The first part of the doctoral work was directed towards the synthesis of the C13-C20 fragment of the peloruside A and to synthesize building blocks with the necessary carbon framework to construct C1-C9 backbone of the molecule. The second part of the research has focused on the synthesis of daphnicyclidin D. A search for new methodology to construct the hexasubstituted fulvene core of the molecule led to investigation of the nature of electrocyclic ring closures of pentadienyl anions in a cascade reaction in which the requisite pentadienyl systems are generated through the initial carbolithiation of carbocyclic trienes. NMR analysis and computational studies has led to an understanding the mechanism of this process. Applications of this reaction cascade towards the synthesis of capnellene and daphnicyclidin D have been initiated.