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ENZYME

ENZYME entry: EC 2.5.1.17

Accepted Name
corrinoid adenosyltransferase
Alternative Name(s)
aquacob(I)alamin adenosyltransferase
aquocob(I)alamin vitamin B12s adenosyltransferase
ATP:cob(I)alamin Cobeta-adenosyltransferase
ATP:corrinoid adenosyltransferase
cob(I)alamin adenosyltransferase
cob(I)yrinic acid a,c-diamide adenosyltransferase
Reaction catalysed
  • 2 ATP + 2 cob(II)alamin + reduced [electron-transfer flavoprotein] = 2 adenosylcob(III)alamin + 3 H(+) + oxidized [electron-transfer flavoprotein] + 2 triphosphate
  • 2 ATP + 2 cob(II)yrinate a,c diamide + reduced [electron-transfer flavoprotein] = 2 adenosylcob(III)yrinate a,c-diamide + 3 H(+) + oxidized [electron-transfer flavoprotein] + 2 triphosphate
Comment(s)
  • The corrinoid adenosylation pathway comprises three steps: (i) reduction of Co(III) to Co(II) by a one-electron transfer.
  • This can occur non-enzymically in the presence of dihydroflavin nucleotides or reduced flavoproteins.
  • (ii) Co(II) is bound by corrinoid adenosyltransferase, resulting in displacement of the lower axial ligand by an aromatic residue.
  • The reduction potential of the 4-coordinate Co(II) intermediate is raised by ~250 mV compared with the free compound, bringing it to within physiological range.
  • This is followed by a second single-electron transfer from either free dihydroflavins or the reduced flavin cofactor of flavoproteins, resulting in reduction to Co(I).
  • (iii) the Co(I) conducts a nucleophilic attack on the adenosyl moiety of ATP, resulting in transfer of the deoxyadenosyl group and oxidation of the cobalt atom to Co(III) state.
  • Three types of corrinoid adenosyltransferases, not related by sequence, have been described.
  • In the anaerobic bacterium Salmonella enterica they are encoded by the cobA gene (a housekeeping enzyme involved in both adenosylcobalamin de novo biosynthesis and salvage), the pduO gene (involved in (S)-propane-1,2-diol utilization), and the eutT gene (involved in ethanolamine utilization).
  • Since EutT hydrolyzes triphosphate during catalysis, it is classified as a separate enzyme.
  • The mammalian enzyme belongs to the PduO type.
  • The enzyme can act on other corrinoids, such as cob(II)inamide.
  • Formerly EC 1.16.8.1.
Cross-references
BRENDA2.5.1.17
EC2PDB2.5.1.17
ExplorEnz2.5.1.17
PRIAM enzyme-specific profiles2.5.1.17
KEGG Ligand Database for Enzyme Nomenclature2.5.1.17
IUBMB Enzyme Nomenclature2.5.1.17
IntEnz2.5.1.17
MEDLINEFind literature relating to 2.5.1.17
MetaCyc2.5.1.17
Rhea expert-curated reactions2.5.1.17
UniProtKB/Swiss-Prot
P45515, ATR_CITFRP0A9H6, BTUR_ECOL6P0A9H5, BTUR_ECOLI
P31570, BTUR_SALTYQ9I472, COBO_PSEAEP29930, COBO_SINSX
O34899, PDUO_BACSUP64804, PDUO_MYCBOP53523, PDUO_MYCLE
P9WP98, PDUO_MYCTOP9WP99, PDUO_MYCTU

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