Pergamon
0040-4039(95)02069-1
Tetrahedron Letters, Vol. 37, No. 1, pp. 9-12, 1996
Copyright © 1995 Elsevier Science Lid
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0040-4039/96 $15.00 + 0.00
Synthesis of 8-Oxo-7,8-Dihydro-6-O-Methyl-2'-Deoxyguanosine and its use
as a Probe to Study DNA-Base Excision by MutY Enzyme
Chamakura V. Varaprasad, Nickolai Bulychev, Arthur P. Grollman and Francis Johnson*
Department of Pharmacological Sciences, School of Medicine, Health Sciences Center
State University of New York at Stony Brook, Stony Brook NY 11794-8651
Abstract: A 23mer oligomer containing 8-oxo-7,8-dihydro-6-O-methyl-2'-deoxyguanosine (1) has been
synthesized from 2'-deoxyguanosine. The activity o1 MutY protein toward this and a related oligomer
containing 8-methoxy-dG has been studied.
Oxidative stress to DNA has emerged as one of the most important events that leads to a number of human
diseases including cancer. It is known that DNA is constantly under attack by reactive oxygen species
generated during normal cell metabolism. Cellular defense mechanisms against such damage include
antioxidants such as uric acid, ascorbic acid and B-carotene and a number of enzymes including superoxide
dismutase, catalase and glutathione peroxidase. Despite these defenses, damage still occurs and is
characterized by a number of oxidized pyrimidine and purine bases of which 8-oxo-7,8-dihydro-2'-
deoxyguanosine 21(8-oxo-dG) has emerged as one of the most significant. An important mechanism of repair
of such potentially mutagenic lesions is the base - excision pathway. In E. Coli for example the damaged base 2
is efficiently repaired by a triad of proteins derived from genes designated as mutM, mutY and mutT. The
enzymatic excision of damaged bases is arguably dependent on the recognition of the oxidative lesions and
the binding efficiency of the specific enzymes to the DNA. In a previous paper 2 we have outlined a mechanism
O°e
H2N H2N
N O N O
.o- ow
I I
OH OH
1 2
by which MutM protein effects base excision in the case of 8-oxo-dG. In continuing studies on these
enzymes we have synthesized the title compound and incorporated it into a pyrimidine rich oligomer [5'-
CTCTCCCTTCXCTCCTTTCCTCT- 3', (!); where X = 8-oxo-7,8-dihydro-6-O-methyl-2'-deoxyguanosine
(1)] with the objective a) of examining the mechanism by which MutY protein effects glycosidic bond
cleavage of the normal base (dA), in the mismatch pair dA:8-oxo-dG, and b) to understand the enzymatic
recognition aspects of this type of damage. This letter describes the details of the synthesis of the above