C-C bond formation frequently serves as a critical step in a variety of metabolic pathways. While two electron mechanisms are well known for carbon skeleton formation of metabolites in Nature, studies in the past decade by us and others have revealed many pathways that employ radical mechanisms. Most of these reactions are catalyzed by radical SAM (S-adenosyl-L-methionine) enzymes, an emerging group of enzymes that catalyze mechanistically unique and diverse free radical-mediated reactions. Since C-C bond formation is frequently the key step in the pathway, functional and mechanistic characterization of these enzymes frequently provides breakthroughs in our understanding of the pathway. In this symposium, we will describe our recent progress on understanding the role of radical chemistry in the biosynthesis of molybdenum cofactor and antifungal nucleoside natural products.

Radical-mediated C–C bond formation in natural product and cofactor biosynthesis

2019 Fall National Meeting

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