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Deconvoluting the Reactivity of Two Intermediates Formed from Modified Pyrimidines

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journal contribution
posted on 19.02.2016, 03:14 authored by Liwei Weng, Sonia M. Horvat, Carl H. Schiesser, Marc M. Greenberg
Generation of the 5-(2′-deoxyuridinyl)methyl radical (6) was reexamined. Trapping by 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl confirms that 6 is generated. However, trapping by methoxyamine reveals that the respective carbocation (10) is also produced. Examining the effects of these traps on products in DNA reveals that the carbocation and not 6 yields interstrand cross-links. Cross-link formation from the carbocation is consistent with DFT calculations that predict that addition at the N1 position of dA is essentially barrierless.