The total synthesis of dolabelide A, and Synthesis of catalysts for the silylation of alcohols, and Invention of a bis-nucleophile for convergent synthesis of 1,3 diol natural products

The total synthesis of the marine natural product dolabelide A was achieved using a synthetically convergent and efficient strategy. The synthesis utilized a cyanohydrin acetonide alkylation to effect a key coupling in the synthesis. A boron mediated aldol reaction was bravely used to complete construction of the carbon skeleton. Spectroscopic data obtained for the synthetic material was consistent with that of the authentic natural product.; Optically active sulfonamide catalysts were synthesized in order to investigate the viability of enantioselective silylation of racemic alcohols. The catalysts did not provide enantioselectivity in silylation, but were quite effective in promoting silylation of alcohols in general. Data was obtained in the study which indicated sulfonamide structures catalyze silylation with HMDS by acting as appropriate proton sources.; An enantiomerically pure bis-nucleophile was invented for its use in the convergent construction of natural products composed of 1,3 diols. A route was developed for the rapid synthesis of this bis-nucleophile. In addition, model studies were accomplished to demonstrate the potential utility of this bis-nucleophile in segment couplings for natural product synthesis.