Mechanistic studies in the radical induced DNA strand cleavage - Formation and reactivity of the radical cation intermediate

摘要

In order to understand the heterolytic cleavage of 4'-DNA radical 1 and the regioselective attack of nucleophiles at the intermediate DNA radical cation 3, the chemistry of model radical 8 was studied. It turned out that the heterolytic cleavage in water is favored over homolysis because of the effective solvation of the ions 9 and 10. The regioselectivity of the nucleophilic attack at radical cation 10 can be explained with the valence bond configuration mixing (VBCM) model. (C) 2000 Elsevier Science Ltd. All rights reserved. [References: 58]