Issue 19, 2004
From the journal:

Organic & Biomolecular Chemistry

Dissociative electron transfer to and from pyrimidine cyclobutane dimers: An electrochemical study

Fabien Boussicault,a   Oliver Krüger,b   Marc Robert*a  and  Uta Wille*c  

* Corresponding authors

a Laboratoire d'Electrochimie Moléculaire, UMR - CNRS No 7591, Université de Paris 7 - Denis Diderot, 2 place Jussieu, Paris Cedex 05, France
E-mail: robert@paris7.jussieu.fr
Fax: + 33 1 44 27 76 25

b Institut für Organische Chemie, Universität Kiel, Olshausenstr. 40, Kiel, Germany

c School of Chemistry, The University of Melbourne, Victoria, Australia
E-mail: uwille@unimelb.edu.au

Abstract

Cyclic voltammetry was used to study the reduction and oxidation behaviour of several pyrimidine cyclobutane dimers mimicking UV induced lesion in DNA strands in polar solvents (N,N-dimethylformamide and acetonitrile). Both electron injection and removal to and from the dimers, respectively, lead to their cleavage and reformation of the monomeric base. The influence of stereochemistry and substitution pattern at the cyclobutane motif on the reactivity has been studied. It appears that the repair process always proceeds in a sequential fashion with initial formation of a dimer ion radical intermediate, which then undergoes ring opening by homolytic cleavage of the two C–C bonds. Standard redox potentials for the formation of both radical anion and radical cation state of the dimers were determined. Quantum calculations on simplified model compounds reveal the reason for the finding that the exergonic homolytic cleavages of the carbon–carbon bonds are endowed with sizeable activation barriers. The consequences of these mechanistic studies on the natural enzymatic repair by photolyase enzyme are discussed.

Graphical abstract: Dissociative electron transfer to and from pyrimidine cyclobutane dimers: An electrochemical study

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Article information

DOI
https://doi.org/10.1039/B406923D
Article type
Paper
Submitted
10 May 2004
Accepted
15 Jul 2004
First published
31 Aug 2004

Org. Biomol. Chem., 2004,2, 2742-2750

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Dissociative electron transfer to and from pyrimidine cyclobutane dimers: An electrochemical study

F. Boussicault, O. Krüger, M. Robert and U. Wille, Org. Biomol. Chem., 2004, 2, 2742 DOI: 10.1039/B406923D

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