A decarboxylation reaction of carboxylic acids allows us to use benzoic acids as coupling partners to generate more complex products through coupling reactions. This strategy has many advantages since benzoic acids are cheaper and more stable than typical organometallic coupling partners. There are some challenges, however, and decarboxylation reactions are often limited to specific classes of benzoic acids, such as ortho-nitrobenzoic acids or perflurobenzoic acids. Our most recent work in this area has uncovered the origin of this ‘ortho-nitro effect’ and shown that the rates of decarboxylation correlate with the field effect (F), a proximity polar effect of the benzoate substituents.



Our ongoing work is focused on identifying and understanding the underlying structural and electronic features that comprise the field effect. Our approach involves the systematic investigation of a broad array of nitro-substituted silver- and copper-carboxylates to understand how carboxylate features, such as aromaticity and structural flexibility, influence decarboxylation. Our long-term goal in this area is to move away from substrate-based control and toward the design of catalysts that promote reactivity through ligand-based field effects, overcoming the existing limitations in the field.

The decarboxylative coupling of benzoic acids with amines would provide an efficient route to aniline and heteroaryl amine products.  Primary anilines are important substructures found in pharmaceuticals, agrochemicals, and functional materials, and also serve as important building blocks in synthesis. Unfortunately, current methods for their preparation often require specialized catalysts or hazardous reagents. We have recently developed a new decarboxylative amination reaction that uses a commercially-available electrophilic amination agent, NFSI, as both the amine source and the oxidant to generate primary amines directly in a single step. Our new reaction offers a direct route to anilines that avoids the need for specialized catalysts, prefunctionalized starting materials and commonly employed hazardous reagents enabling more rapid and efficient access to these key scaffolds in synthesis.