Coenzymes

Coenzyme A

• Forms thioesters with carboxylic acids

• Thioesters can be attacked by

electrophiles to form addition
compounds and by nucleophiles to
displace --SCoA.
Thiamine pyrophosphate
• Derived from Vit.B1

• α-keto ( oxo) acid decarboxylase,

α-keto acid oxidase,
transketolase and
phosphoketolase enzymes
Potent nucleophile
participating in
covalent catalysis
TPP: Pyruvate decarboxylase
• Catalyzes the production of acetaldehyde from pyruvate
 Pyridoxal phosphate
• Pyridoxine or pyridoxamine, vit. B6.
• Important in amino acid metabolism--
aminotransferase (transaminase),
decarboxylase and racemase reactions.
• Schiff base linkage (-N=CH-) is formed,
involving the aldehyde group of the
coenzyme.
• Phenolic group may help to stabilize the
Schiff base intermediate
Pyridoxal phosphate

Conjugated Positively charged N withdraws

double bond electrons from the α-carbon of
amino acid
Amino acid racemase enzymes
 Pyridoxal phosphate
• The reverse sequence may then take place, initiated by the attack on
pyridoxamine phosphate by a different oxo acid.
• Produces a different amino acid from that initially present.
• Aspartate transaminase mechanism

• Decarboxylase reactions -- Schiff base complex loses the a-carboxyl group

rather than the hydrogen atom
• Resulting complex is then hydrolysed to reform the coenzyme and give an
amine (RCH2NH2).
Tetrahydrofolate
• Derived from folic acid

• Atoms N5 and N10 can carry one-carbon units for transfer

• Formate-tetrahydrofolate ligase catalyzes the addition of formate to
tetrahydrofolate
•
Tetrahydrofolate: Glycine
hydroxymethyltransferase
 Coenzyme B12
• Central core of a cobalt ion surrounded by a
corrin ring
• One of the pyrrole components of the corrin ring
is joined to dimethylbenzimidazole, which co-
ordinates Co from 'below' the ring
• Sixth co-ordination site is believed to be
occupied in vivo by OH-
• Coenzyme forms obtained after activation of
vitamin by NADH-linked reducing systems.

Strongly nucleophilic, can

be alkylated
Methylmalonyl-coA mutase