Radical S-Adenosylmethionine (SAM) Enzymes in Cofactor Biosynthesis: A Treasure Trove of Complex Organic Radical Rearrangement Reactions (original) (raw)

This minireview explores radical S-adenosylmethionine (SAM) enzymes that facilitate the biosynthesis of essential cofactors including thiamin, menaquinone, molybdopterin, coenzyme F420, and heme. A key focus is on the complex radical rearrangements catalyzed by these enzymes, which remain largely unprecedented in traditional organic chemistry. The review highlights the catalytic mechanisms, structural considerations, and the implications of these radical SAM enzymatic reactions in primary metabolism.