Esterification reactions are central to many aspects of industrial and biological chemistry. The formation of carboxyesters typically occurs through nucleophilic attack of an alcohol onto the carboxylate carbon. Under certain conditions employed in organic synthesis, the carboxylate nucleophile can be alkylated to generate esters from alkyl halides, but this reaction has only been observed transiently in enzymatic chemistry. Here, we report a new carboxylate alkylating enzyme – BrtB – that catalyzes O-C bond formation between free fatty acids and the secondary alkyl halide moieties found in the bartolosides. Guided by this novel reactivity, we uncovered a variety of natural fatty acid-bartoloside esters, the likely end-products of bartoloside biosynthetic gene clusters.
Preprint Reis et al 2019 SI