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Metallocene - DNA: Synthesis, molecular and electronic structure and DNA incorporation of C5-ferrocenylthymidine derivatives

Lookup NU author(s): Dr Andrew Pike, Lyndsey Ryder, Dr Ben Horrocks, Emeritus Professor Bill Clegg, Dr Mark Elsegood, Professor Bernard Connolly, Professor Andrew Houlton

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Abstract

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.


Publication metadata

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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