Formyl transfer reactions play a key role in the construction of the p
urine heterocycle during de novo purine biosynthesis. Formylation is c
atalyzed early in the pathway by the purN glycinamide ribonucleotide t
ransformylase (GAR Transformylase, EC 2.1.2.2) in a tetrahydrofolate-d
ependent manner and also by the purT GAR transformylase in a tetrahydr
ofolate-independent manner in bacteria. Late in the pathway, 5-aminoim
idazole-4-carboxamide ribonucleotide transformylase (AICAR Transformyl
ase, EC 2.1.2.3) catalyzes the second and final formylation involved i
n purine nucleotide biosynthesis. This article summarizes the salient
properties and mechanistic knowledge on the transformylases with speci
al emphasis on the mechanism of the purN GAR transformylase as explore
d by mutagenesis studies.