Oxidative cleavage of a cyclobutane pyrimidine dimer by photochemically generated nitrate radicals (no(3)*).
[reaction: see text] Photochemically generated nitrate radicals (NO(3)(*)) cleave the stereoisomeric N,N-dimethyl-substituted uracil cyclobutane dimers 1a-d into the monomeric uracil derivative 2 as the major reaction pathway. A preferred splitting of the syn dimers 1a,b was observed. The reaction is expected to proceed through initial one-electron oxidation with formation of an intermediate cyclobutane radical cation 11. In addition to cycloreversion, competing reaction steps of 11, which lead to the observed byproducts, are suggested.
Krüger
O
O
Institut für Organische Chemie der Christian-Albrechts-Universität zu Kiel, Olshausenstr. 40, 24098 Kiel, Germany.
Wille
U
U
D004260:DNA Repair / Q000187:drug effects; D005609:Free Radicals / Q000378:metabolism / Q000494:pharmacology; D009566:Nitrates / Q000378:metabolism / Q000494:pharmacology; D010084:Oxidation-Reduction; D010777:Photochemistry; D011740:Pyrimidine Dimers / Q000378:metabolism*
D005609:Free Radicals; D009566:Nitrates; D011740:Pyrimidine Dimers