A Novel Route to Enantioenriched α-Allyl α-Fluoroketones via Palladium Catalyzed Decarboxylation

Abstract

This thesis details the development of a novel catalytic asymmetric route to α-fluorinated ketones. Enantioenriched α-fluoroketones were produced in good yields and high enantiomeric ratios via palladium-catalyzed decarboxylation of cyclic α-fluorinated β-keto allylic esters. A series of α-fluoroketones were produced to examine the scope and the conditions for this reaction. In contrast to previous routes toward α-fluorinated ketones, this route is advantageous for several reasons. First, this route avoids the issues associated with the regiospecific generation of fluorinated ketone enolates by forming the enolate in situ by palladium-catalyzed decarboxylation. Secondly, this method requires only a catalytic amount of non-racemic material in contrast to chiral fluorinating reagents which are required in stoichiometric amounts. Lastly, the β-keto ester substrates for this reaction are easily synthesized and readily fluorinated by electrophilic fluorinating reagents.