Carbohydrates play a key role in the biological activity of numerous natural products. In many instances, their biosynthesis requires radical mediated chemical transformations, some of which are catalyzed by radical SAM enzymes. DesII is one such enzyme involved in the deamination reaction necessary for the net C4 deoxygenation of a glucose derivative en route to desosamine formation. SpeY has been shown to catalyze dioxane ring formation in a disaccharide. GenK is a cobalamin-dependent radical SAM enzyme that catalyzes the methylation of an unactivated sp3 carbon of GenX2 to produce the intermediate G418 during the biosynthesis of gentamicin. OxsB is another cobalamin-dependent radical SAM enzyme responsible for the ring contraction of 2'-deoxyadenosine 5'-monophosphate to yield the four-membered heterocycle in oxetanocin. These enzymes are representative radical SAM enzymes that are involved in carbohydrate biosynthesis. The biosynthetic roles of some of these enzymes, their mechanisms of catalysis, the questions that have arisen during their study, and the insights they can offer for furthering our understanding of radical SAM enzymology will be discussed in this presentation.

Radical SAM enzymes in the biosynthesis of sugar-containing natural products

255th National Meeting (2018)

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