10.1021/ja9612763.s001
Rex X.-F. Ren
Rex X.-F.
Ren
Narayan C. Chaudhuri
Narayan C.
Chaudhuri
Pamela L. Paris
Pamela L.
Paris
Rumney
Rumney
Eric T. Kool
Eric T.
Kool
Naphthalene, Phenanthrene, and Pyrene as DNA Base
Analogues: Synthesis, Structure, and Fluorescence in DNA
American Chemical Society
1996
α- anomers
compound
1α- chlorodeoxyribose precursor
single-crystal X-ray structure
1 H NOE experiments
β- anomers
1- pyrenyl deoxynucleosides
C-glycosidic bond formation method
DNA
polycyclic C-nucleoside derivatives
Such nucleoside analogues
1996-08-21 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Naphthalene_Phenanthrene_and_Pyrene_as_DNA_Base_Analogues_Synthesis_Structure_and_Fluorescence_in_DNA/4057314
We describe the synthesis, structures, and DNA incorporation of
deoxyribonucleosides carrying polycyclic
aromatic hydrocarbons as the DNA “base” analogue. The new
polycyclic compounds are 1-naphthyl, 2-naphthyl,
9-phenanthrenyl, and 1-pyrenyl deoxynucleosides. The compounds are
synthesized using a recently developed
C-glycosidic bond formation method involving organocadmium derivatives
of the aromatic compounds coupling
with a 1α-chlorodeoxyribose precursor. The principal products of
this coupling are the α-anomers of the
deoxyribosides. An efficient method has also been developed for
epimerization of the α-anomers to β-anomers by
acid-catalyzed equilibration; this isomerization is successfully
carried out on the four polycyclic nucleosides as well
as two substituted phenyl nucleosides. The geometry of the
anomeric substitution is derived from <sup>1</sup>H NOE
experiments
and is also correlated with a single-crystal X-ray structure of one
α-isomer. Three of the polycyclic C-nucleoside
derivatives are incorporated into DNA oligonucleotides via their
phosphoramidite derivatives; the pyrenyl and
phenanthrenyl derivatives are shown to be fluorescent in a DNA
sequence. The results (1) broaden the scope of our
C-glycoside coupling reaction, (2) demonstrate that (using a new
acid-catalyzed epimerization) both α- and β-anomers
are easily synthesized, and (3) constitute a new class of
deoxynucleoside derivatives. Such nucleoside
analogues
may be useful as biophysical probes for the study of noncovalent
interactions such as aromatic π-stacking in DNA.
In addition, the fluorescence of the phenanthrene and pyrene
nucleosides may make them especially useful as structural
probes.