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Pyrrolyl-, 2-(2-thienyl)pyrrolyl- and 2,5-bis(2-thienyl)pyrrolyl-nucleosides: synthesis, molecular and electronic structure, and redox behaviour of C5-thymidine derivatives

Lookup NU author(s): Dr Miguel Galindo-Cuesta, Jennifer Hannant, Dr Ross Harrington, Emeritus Professor Bill Clegg, Dr Ben Horrocks, Dr Andrew Pike, Professor Andrew Houlton

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Abstract

A series of modified nucleosides based on thymidine have been prepared by Pd-catalysed cross-coupling between N-alkyl-alkynyl functionalised pyrrolyl- (py), 2-(2-thienyl)pyrrolyl- (tp) or 2,5-bis(2-thienyl) pyrrolyl (tpt) groups with 5-iodo-2'-deoxyuridine. The length of the alkyl chain linking the nucleoside and pyrrolyl-containing unit, N(CH2)(n) C C-nucleoside (where n = 1-3) was also varied. The compounds have been characterised by H-1 NMR, ES-MS, UV-vis, cyclic voltammetry (CV) and, in some cases, single-crystal X-ray diffraction. Cyclic voltammetry studies demonstrated that all the py-, tp- and tpt-alkynyl derivatives 1-7 can be electrochemically polymerised to form conductive materials. It was found that increasing the N-alkyl chain length in these cases resulted in only minor changes in the oxidation potential. The same behaviour was observed for the tp- and tpt-modified nucleosides 9-12; however, the py-derivative, 8, produced a poorly conducting material. DFT calculations on the one-electron oxidised cation of the modified nucleosides bearing tp or tpt showed that spin density is located on the pyrrolyl and thienyl units in all cases and that the coplanarity of adjacent rings increases upon oxidation. In contrast, in the corresponding pyrrolyl cases the spin density is distributed over the whole molecule, suggesting that polymerisation does not occur solely at the pyrrolyl-Ca position and the conjugation is interrupted.


Publication metadata

Author(s): Galindo MA, Hannant J, Harrington RW, Clegg W, Horrocks BR, Pike AR, Houlton A

Publication type: Article

Publication status: Published

Journal: Organic & Biomolecular Chemistry

Year: 2011

Volume: 9

Issue: 5

Pages: 1555-1564

Print publication date: 01/01/2011

ISSN (print): 1477-0520

ISSN (electronic): 1477-0539

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/c0ob00466a

DOI: 10.1039/c0ob00466a


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