New Catalytic Motifs in Flavoenzymology

Abstract Over the past decade several unanticipated major discoveries have been made in flavoenzymology. These include three new flavin intermediates: prenylated flavin, flavin-N5-oxide, and N5 alkylated flavin. Several novel variants of the flavin-dependent Baeyer-Villiger rearrangement have been reported. The mechanisms of enzymes that use flavin as a substrate—dimethylbenzimidazole synthase, 8-amino flavin synthase and riboflavin lyase have been elucidated. Major progress has also been made on the biosynthesis of the F420 deazaflavin and a remarkable new flavin-dependent photoenzyme has been reported. In this article, we discuss these recent advances with an emphasis on new biosynthetic mechanisms and strategies.