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6 Cards in this Set

  • Front
  • Back
Macrocylic metallocofactors (4)
Cobalamin (Co)
Tetrapyrroles (Ni)
Porphyrins (Fe)
Chlorophyll (Mg)
Metal clusters
Fe-S (Fe4S4, Fe2)
FeMoCo
Cu2, mixed metal clusters
Single metal sites
Non-heme iron
Cu2+
mostly structural sites: Ca2+, Zn2+
The Cobalamin cofactor
- 3 States, most reduced is Cb(1)
- (1,3) are active, (2) is inactive
- Vitamin B12
- Catalyzes three reaction types:
- Intramolecular rearrangements
- Reductions of ribonucleotides to
deoxyribonucleotides (DNA synthesis)
-Methyl group transfers (assisted by
tetrahydrofolate)
General Mechanism for AdoCbl-Dependent Rearrangement Reactions
C-Co bond to generate  5’-DA  radical 

The 5’DA radical mediates H abstraction from substrate  to form the intermediate 5’-DA and substrate radical.
C-Co bond to generate 5’-DA radical

The 5’DA radical mediates H abstraction from substrate to form the intermediate 5’-DA and substrate radical.
Summary: Two Roles of Cobalamins
Adenosyl cobalamin = adenosyl radical

Methyl cobalamin = methyl donor