“…Artificial metalloenzymes (ArMs) 17 represent a particularly interesting source of enzymes for siteselective catalysis since they could be used to impart site selectivity to synthetic catalysts, thus avoiding the blocking and protecting group strategies noted in the introduction. To date, there have been relatively few examples of this capability, 404,405 and these involved the generation of carbene intermediates. The ArM scaffold is primarily involved in binding and orienting substrates relative to these intermediates to impart selectivity, which mimics the mechanisms of P450s, FeDOs, FDHs, and other enzymes that generate intermediates capable of reacting with a range of functional groups and C-H bonds in organic substrates (e.g.…”