Development of Aryl Decarboxylative Functionalization Reactions

Abstract

New synthetic methods are needed to address the tremendous environmental costs associated with fine chemical production. Towards this goal, my graduate research has focused on designing and developing new decarboxylative cross-coupling methods. These reactions replace high energy, unstable, and expensive organometallic nucleophiles with low energy and readily available (hetero)aryl carboxylic acids. First, I reported an efficient palladium catalyzed salt-free decarboxylative allylation of allylic carbonates, which was designed to generate base in-situ. Next, I advanced a method for the decarboxylative cross-coupling of inexpensive aryl chlorides. The mechanism of this transformation was investigated and gave insights that enabled an increase in catalyst performance. More recently, I developed the first gold catalyzed decarboxylative cross-coupling of aryl iodides. This reaction overcame limitations associated both with decarboxylative couplings and reactions involving redox events at gold. I then investigated the mechanism this reaction with the goal of surmounting the current limitations of this promising technology.