Acireductone dioxygenases (ARDs) catalyze the oxidative cleavage of aliphatic carbon-carbon bonds of a substrate found at the only branch point in the ubiquitous methionine salvage pathway. Notably, the regioselectivity of this reaction depends on the nature of the metal ion present within the active site of the enzyme (Fe(II) (ARD') or Ni(II) (ARD)). In our most recent studies, we have discovered ARD'-type reactivity in reactions involving exposure of an in situ generated Fe(II) acireductone complex to dioxygen. Spectroscopic studies and product analysis of this reaction will be described, along with relevant comparative reactions.

Iron-promoted oxidative aliphatic carbon-carbon bond cleavage: Relevance to acireductone dioxygenases

244th National Meeting (2012)

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