%0 Generic
%9 Doctoral Dissertation
%A Poniatowski, Alexander James
%D 2009
%F pittir:9067
%K cytotoxin; macrolactone; macrolide lactone; tetrahydropyrone
%T Radical Cations in Synthesis: Utilizing an Electron Transfer-Initiated Cyclization Toward the Natural Product Apicularen A
%U http://d-scholarship-dev.library.pitt.edu/9067/
%X Reported herein is a synthetic campaign toward the vacuolar ATPase inhibitor apicularen A through an oxidative cyclization protocol. In this protocol (termed Electron Transfer-Initiated Cyclization, or ETIC), highly reactive oxocarbenium ions are generated through benzylic carbon-carbon σ-bond cleavage under chemically mild conditions. Regioselective cleavage of one homobenzylic ether in the presence of another homobenzylic ether is achieved by selectively weakening one carbon-carbon σ-bond through substitution. This work demonstrates that if bond cleavage is sufficiently rapid following oxidation, then oxidative fragmentation reactions can be used to generate stable cations selectively in the presence of other readily oxidized functional groups