Evolved enzymes carry out new-to-nature radical chemistry

P450 enzymes have been trained to carry out unnatural asymmetric radical cyclisation reactions. By showing that enzymes can direct the stereochemistry of a free-radical process, the findings offer a potential solution to what the researchers behind the work describe as a ‘notoriously difficult’ challenge.

The US team from the University of California, Santa Barbara, and the University of Pittsburgh, repurposed a cytochrome P450 metallozyme, which normally carries out stereoselective oxidation reactions, to perform an atom-transfer radical cyclisation reaction (ATRC). These ATRC reactions have previously only been performed unselectively using small molecule catalysts.