Ribonucleotide reductases (RNRs) catalyze the conversion of both purine and
pyrimidine nucleotides to deoxynucleotides in all organisms and provide al
l the monomeric precursors essential for both DNA replication and repair. R
NRs have been divided into three classes on the basis of their unique metal
lo-cofactors. The exquisitely controlled free radical chemistry used by all
RNRs, and the commonality of the structures of the subunits where the nucl
eotide reduction process occurs, together provide compelling evidence for t
he importance of chemistry in the divergent evolution of RNRs from a common
progenitor.