A zero-length diazirine photoactive nucleoside

Article abstract of DOI:10.1081/NCN-120022617

The scheme of synthesis which allows to obtain 5-(3H-diazirin-3-yl)-2′-deoxyuridine as the zero-length photoactive nucleoside is described.

Full text of DOI:10.1081/NCN-120022617

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Nucleosides, Nucleotides and Nucleic Acids
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A Zero-Length Diazirine Photoactive Nucleoside
M. Taranenko a , M. Mtchedlidze a , N. Sumbatyan a & G. Korshunova b
a Chemistry Department , Moscow, Leninskie gory, Russia
b Belozersky Institute of Physico-Chemical Biology, Moscow State University , Moscow,
Leninskie gory, Russia
Published online: 31 Aug 2006.
To cite this article: M. Taranenko , M. Mtchedlidze , N. Sumbatyan & G. Korshunova (2003) A Zero-Length Diazirine
Photoactive Nucleoside, Nucleosides, Nucleotides and Nucleic Acids, 22:5-8, 715-717, DOI: 10.1081/NCN-120022617
To link to this article: http://dx.doi.org/10.1081/NCN-120022617
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NUCLEOSIDES, NUCLEOTIDES & NUCLEIC ACIDS
Vol. 22, Nos. 5–8, pp. 715–717, 2003
A Zero-Length Diazirine Photoactive Nucleoside
M. Taranenko,1 M. Mtchedlidze,1 N. Sumbatyan,1 and G. Korshunova2
1Chemistry Department and
2Belozersky Institute of Physico-Chemical Biology,
Moscow State University, Moscow,
Leninskie gory, Russia
ABSTRACT
The scheme of synthesis which allows to obtain 5-(3H-diazirin-3-yl)-20-deoxyuri-
dine as the zero-length photoactive nucleoside is described.
Nucleic acid analogs bearing a photoreactive diazirine moiety have been success-
fully used for photoaffinity labeling of proteins. A number of photoreactive nucleic
acid analogs containing nucleotides, which were connected by different length
spacers with diazirine group were synthesized and used for investigations of nucleic
acid-protein interactions.[1,2] However, it is desirable to have a photoactive nucleo-
side with diazirine function of minimal length and volume. Cross-linking affected
by this type reagent may be more selective and such photoprobe should be useful
for structural analysis and for investigation of close contacts nucleic acid-protein.
We report the synthesis of a new photoactive derivative of deoxyuridine, which
contain diazirine cycle at position 5 of the uracyl ring (I). The synthesis was carried
out according to the scheme shown below, starting from dT (II). Acetyl groups were
chosen for protecting hydroxyl sugar functions. Oxidation of the methyl group of the
thymidine derivative (III) by potassium peroxydisulphate in the presence of catalytic
amounts of copper ions in aqueous acetonitrile yielded 5-formyluridine (IV).[3] The
Schiff’s base (V) was prepared by the reaction of the aldehyde (IV) with tert-butyl-
amine in dry dioxane in the presence of molecular sieves for 24 h at room
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DOI: 10.1081/NCN-120022617
Copyright # 2003 by Marcel Dekker, Inc.
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Taranenko et al.
temperature. Formation of the diaziridine ring in compound (VI) was accomplished
by the action of hydroxylamine-O-sulfonic acid in ethanol-water mixture (3:1) for
2–3 h at 0–4ꢀC. Conversion of this intermediate (VI) to diazirine (I) was achieved
by oxidation with tert-butylhypochlorite for 16 h at 0–4ꢀC.[4] The presence of diazir-
ine group in compound (I) was proved by thin layer chromatography. Under UV-
light irradiation (366 nm) the spot corresponding to diazirine nucleoside formed
the covalent bond with silicagel plate.
ACKNOWLEDGMENT
This investigation was supported by the Russian Foundation for Basic
Research.
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Zero-Length Diazirine Photoactive Nucleoside
717
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