Deconvoluting the reactivity of two intermediates formed from modified pyrimidines
| Autor: | Carl H. Schiesser, Marc M. Greenberg, Liwei Weng, Sonia M. Horvat |
|---|---|
| Rok vydání: | 2013 |
| Předmět: |
Molecular Structure
Chemistry Radical Organic Chemistry Methyl radical Trapping Carbocation Cleavage (embryo) Photochemistry Biochemistry Deoxyuridine Article Cyclic N-Oxides chemistry.chemical_compound Cross-Linking Reagents Pyrimidines Methoxyamine Molecule Reactivity (chemistry) Spin Labels Physical and Theoretical Chemistry |
| Zdroj: | Organic letters. 15(14) |
| ISSN: | 1523-7052 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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