Oxo-acid dehydrogenase complexes

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Note 1: The acyl group on the dihydrolipoyl group of EC 2.3.1.12 moves rapidly between S-8 and S-6, with more on S-8 at equilibrium.

Note 2: E1 (EC 1.2.4.1, EC 1.2.4.2 or EC 1.2.4.4) contains thiamine diphosphate

The N⁶-lipoyllysine residues of E2 (EC 2.3.1.12, EC 2.3.1.61 and EC 2.3.1.168) are the substrates reductively acylated by EC 1.2.4.1, EC 1.2.4.2, and EC 1.2.4.4 respectively.

The overall reaction is:

R-CO-COO^- + NAD⁺ + HS-CoA = R-CO-S-CoA + NADH + CO₂

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citric acid cycle
EC 1.2.4.1 pyruvate dehydrogenase (acetyl-transferring)
EC 1.2.4.2 oxoglutarate dehydrogenase (succinyl-transferring)
EC 1.2.4.4 3-methyl-2-oxobutanoate dehydrogenase (2-methylpropanoyl-transferring)
EC 1.8.1.4 dihydrolipoyl dehydrogenase
EC 2.3.1.12 dihydrolipoyllysine-residue acetyltransferase
EC 2.3.1.61 dihydrolipoyllysine-residue succinyltransferase
EC 2.3.1.168 dihydrolipoyllysine-residue (2-methylpropanoyl)transferase