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The radical SAM superfamily of metalloproteins catalyze the reductive cleavage of S-adenosyl-l-methionine to generate a 5′-deoxyadenosyl radical (5′-dA) intermediate that is obligate for turnover. The 5′-dA acts as a potent oxidant, initiating turnover by abstracting a hydrogen atom from an appropriate substrate. A special class of these enzymes use this strategy to functionalize unactivated C–H bonds...
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