This research is being funded by the Organic Synthesis Chemistry Program. It is a continuation of research in the same area. Dr. Hoffman has developed the chemistry of a group of compounds that permits the highly flexible synthesis of number of important classes of structures such as amino acids and heterocycles. These reactions have the potential to simplify the synthesis of otherwise difficultly obtainable substances. The use of 2-sulfonyloxy carbonyl compounds in synthesis has received considerable attention in recent years. 2-Sulfonyloxy carbonyl compounds (ketones and esters) can be prepared readily from enol derivatives of carbonyl compounds, and the sulfonyloxy group introduces distinct reactivity to the product. Of greatest interest is that 2-sulfonyloxy carbonyl compounds undergo very clean nucleophilic substitution. This propensity has been exploited in simple 2-sulfonyloxy ketones and esters as a means to synthesize 2-substituted ketones and unusual amino acid esters. The planned work involves the synthesis of selected, new 2-sulfonyloxy carbonyl compounds, and exploits their special reactivity for the preparation of densely functionalized products. Three specific objectives are set: a) to develop methodology for the synthesis of chiral 3-hydroxy-2-nosyloxy esters and their elaboration into chiral 1,2,3-trifunctionalized compounds, b) to develop the use of unsaturated nosyloxy esters for the synthesis of unsaturated ester derivatives, and c) to continue studies on the electrophilic addition to enamine and enol derivatives of 2-ketoesters.
