Methylmalonylcarba(dethia)‐Coenzyme A as Substrate of the Coenzyme B₁₂‐Dependent Methylmalonyl‐CoA Mutase: Enzymatic Rearrangement of a β‐ to a γ‐Keto Acid

Coenzyme A analogues with CH2 instead of S are model compounds that may be used to gain insight into the mechanism of action of methylmalonyl-CoA mutase. Propionylcarba(dethia)coenzyme A 1 was synthesized and enzymatically carboxylated to the methylmalonate derivative 2. The coenzyme B12-dependent enzymatic rearrangement of the β-keto acid 2 to the γ-keto acid 3 is the first of its kind to be described.