Making and breaking carbon-carbon bonds in class C radical SAM methyltransferases

Radical S-adenosylmethionine (SAM) enzymes utilize a [4Fe-4S]1+ cluster and S-(5′-adenosyl)-L-methionine, (SAM), to generate a highly reactive radical and catalyze what is arguably the most diverse set of chemical reactions for any known enzyme family. At the heart of radical SAM catalysis is a highly reactive 5′-deoxyadenosyl radical intermediate (5′-dAdo●) generated through reductive cleavage of SAM or nucleophilic attack of the unique iron of...