The complete stereochemistry of the enzymatic dehydration of 4-hydroxybutyryl coenzyme A to crotonyl coenzyme A.

4-Hydroxybutyryl coenzyme A (4-hydroxybutyryl-CoA, 1, Scheme 1) contains three diastereotopic methylene groups which either lose or gain a hydrogen atom during the reversible dehydration to crotonyl-CoA (but-2-enoyl-CoA, 2). 4-Hydroxybutyryl-CoA dehydratase from Clostridium aminobutyricum, which catalyzes this intriguing g elimination of water, has been shown to be also involved in the recently discovered fifth CO2 fixation cycle. [2] Each 56-kDa subunit of the homotetrameric enzyme contains one flavin adenine dinucleotide (FAD) and a [Fe4S4] 2+ cluster. The crystal structure reveals a cleft between the cluster and FAD in which the substrate can be bound. The medium-chain acyl-CoA dehydrogenase, which also contains FAD but no [Fe4S4] 2+

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