UC Davis

The allylation reaction is an ambiphilic reaction depending on the nature of the allylic substituent. Depending on the allylic substituent the allyl can either be nucleophilic or electrophilic. This dissertation describes the nucleophilic crotylation of a-chiral alkoxy imines in high diastereoselectivity and the electrophilic enantioselective allylation of a prochiral heterocyclic sulfonimidamide in high enantioselectivity and yield. Chapter 1 describes the Lewis acid promoted addition of prochiral E and Z allyl nucleophiles to chiral a-alkoxy N-tosyl imines is described. Alkene geometry is selectively transferred to the newly formed carbon-carbon bond, resulting in stereochemical control of carbons 2 and 3, resulting in 2-alkoxy-3-N-tosyl-4-alkyl-5-hexene products. A computational analysis to elucidate the high selectivity is also presented. This methodology was employed in the synthesis of two naturally occurring isomers of clausenamide. Chapter 2 describes the enantioselective allylation of prochiral sulfonimidamides via a Tsuji-Trost Asymmetric Allylation reaction. Sulfonimidamides undergo prototropic tautomerization in solution. In the case where both nitrogen substituents of a disubstituted sulfonimidamide are the same, the two tautomers are also enantiomers, allowing deprotonation to generate a prochiral anion. Herein we report the first transition metal catalyzed approach to the desymmetrization of sulfonimidamides relying on commercially available palladium catalysts and ligands. The reaction leads to functionalized, enantioenriched products in high yields.