Interdisciplinary Centre of Marine and Environmental Research (CIIMAR/CIMAR), University of Porto, Avenida General Norton de Matos, s/n, 4450-208, Matosinhos, Portugal.
Nat Commun. 2020 Mar 19;11(1):1458. doi: 10.1038/s41467-020-15302-z.
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 carboxylate alkylating enzyme - BrtB - that catalyzes O-C bond formation between free fatty acids of varying chain length and the secondary alkyl halide moieties found in the bartolosides. Guided by this reactivity, we uncovered a variety of natural fatty acid-bartoloside esters, previously unrecognized products of the bartoloside biosynthetic gene cluster.
酯化反应是许多工业和生物化学领域的核心反应。羧酸酯的形成通常通过醇对羧酸根碳的亲核攻击来实现。在有机合成中采用的某些条件下，羧酸根亲核试剂可以被烷基化，从而将卤代烷烃转化为酯，但这种反应仅在酶化学中短暂观察到。在这里，我们报告了一种羧酸酯烷基化酶 - BrtB -，它可以催化不同链长的游离脂肪酸与 bartolosides 中发现的次级烷基卤化物部分之间的 O-C 键形成。受这种反应性的启发，我们发现了各种天然脂肪酸-bartoloside 酯，这是 bartoloside 生物合成基因簇的先前未被识别的产物。
