Elaborations of unactivated carbon centers are among the most demanding reactions that enzymes catalyze. These reactions generally involve radical intermediates, often produced by strategic abstraction of substrate hydrogen atoms (H�s). A distinct strategy, predominant in the anaerobic world and also important in aerobes, employs a 5'-deoxyadenosine 5'-radical (5'-dA�), derived from a reductive cleavage of S-adenosylmethionine, as the H� abstractor. In all enzymatic reactions in which H� abstraction from an unactivated carbon center has been demonstrated unequivocally, the carbon center has been sp3-hybridized. However, reactions involving the functionalization of sp2-hybridized carbons centers are increasingly observed, especially within the radical SAM superfamily of enzymes. This talk will highlight strategies employed by radical SAM enzymes to functionalize sp2-hybridized carbon centers, with particular focus on two enzymes, RlmN and Cfr, that methylate carbons 2 and 3, respectively, of 23S rRNA.

Radical-dependent enzymatic functionalization of sp<sup>2</sup>-hybridized carbon centers

245th National Meeting (2013)

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Radical-dependent enzymatic functionalization of sp2-hybridized carbon centers

Radical-dependent enzymatic functionalization of sp²-hybridized carbon centers