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Lookup NU author(s): Dr Andrew Pike, Lyndsey Ryder, Dr Ben Horrocks, Professor William Clegg, Dr Mark Elsegood, Professor Bernard Connolly, Professor Andrew HoultonORCiD
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Ferrocenylthymidine derivatives have been prepared by Pd-catalysed cross-coupling between ethynylferrocene or vinylferrocene and 5-iodo-2′-deoxyuridine. In the latter case a mixture of trans (2a) and gem (2b) isomers was obtained. The cis-vinylferrocenyl (2c), and ethylferrocenyl (3) derivatives were obtained by catalytic hydrogenation of ethynylferrocenyl-dT (1a), and 2c respectively. Single-crystal x-ray data for 1a, the ferrocenyl-2′furano-pyrimidone 1b, and 2a show that the nucleobase is essentially co-planar with the substituted Cp ring of the metallocene. The selective reduction of the linkage between the ferrocenyl and thymidine moieties, from -C≡C- to -CH2CH2-, causes a shift in the reduction potential of - 124 mV. DFT calculations for the one-electron oxidised species indicate that the diminished conjugation reduces the spin transfer onto the bridging C2 group, but has less effect on the extent transferred to the nucleobase from the ferrocenyl group. Compound la was incorporated site-specifically into DNA oligonucleotides by using automated solid-phase methods. However, some interconversion of 1a → 1h occurs, even under rapid mild conditions of deprotection.
Author(s): Pike AR, Ryder LC, Horrocks BR, Clegg W, Elsegood MRJ, Connolly BA, Houlton A
Publication type: Article
Publication status: Published
Journal: Chemistry: A European Journal
Year: 2002
Volume: 8
Issue: 13
Pages: 2891-2899
ISSN (print): 0947-6539
ISSN (electronic): 1521-3765
Publisher: Wiley - V C H Verlag GmbH & Co. KGaA
URL: http://dx.doi.org/10.1002/1521-3765(20020703)8:13<2891::AID-CHEM2891>3.0.CO;2-B
DOI: 10.1002/1521-3765(20020703)8:13<2891::AID-CHEM2891>3.0.CO;2-B
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