%0 Generic
%9 Doctoral Dissertation
%A Caplan, Scott
%D 2019
%F pittir:35517
%K natural products, cycloadditions, macrocycles, oxidation, oxygen heterocycles
%T Total Synthesis of Divergolides E and H and an Investigation into the Oxidative Rearrangement to Divergolides C and D
%U http://d-scholarship-dev.library.pitt.edu/35517/
%X This thesis describes the first total syntheses of divergolides E and H. Construction of the core bridged bicyclic acetal unit was accomplished using a hetero-Diels–Alder (HDA) reaction and oxidative carbon-hydrogen bond cleavage to couple two highly functionalized subunits. Additional highlights of this convergent synthesis include a chelation-controlled alkenylzinc addition, amide formation between a hindered aniline and an acylating agent prone to ketene formation, and a challenging macrolactonization. Model studies showed effective oxidation of the core structure using a hypervalent iodine species which sets the stage for rearrangement into divergolides C and D.