Fluoropyruvate: an unusal substrate for Escherichia coli pyruvate dehydrogenase.

The pyruvate dehydrogenase component of the $\text{E. coli}$ pyruvate dehydrogenase complex catalyzes the decomposition of 3-fluoropyruvate to acetate and fluoride ions in equimolar amounts and at about one-tenth the rate at which it catalyzes the conversion of pyruvate and ferricyanide to acetate and ferrocyanide. When the reaction is carried out in [³H]H₂O the product is [³H]acetate. The reaction is strictly dependent upon added thiamin pyrophosphate, and a mechanistic role is proposed for this coenzyme.