Synthesis and reaction of 4'-hydroperoxynucleosides. A model for oxidative degradation of DNA by action of bleomycins.
The reaction of 1-(3-O-benzoyl-2,5-dideoxy-beta-D-glycero-pent-4-enofuranosyl)t hym ine (1a) with anhydrous hydrogen peroxide in the presence of a catalytic amount of trifluoroacetic acid leads to the formation of 3'-O-benzoyl-5'-deoxy-4'-hydroperoxythymidines (2a) and (3a). It has been demonstrated that the hydroperoxide 2a is capable of undergoing a Criegee-type rearrangement to lead ultimately to thyminylpropenal, whereas the reduction of 2a gives free thymine exclusively.
D001761:Bleomycin; D055598:Chemical Phenomena; D002621:Chemistry; D008956:Models, Chemical; D010084:Oxidation-Reduction; D010545:Peroxides; D013936:Thymidine / Q000031:analogs & derivatives* / Q000138:chemical synthesis
D010545:Peroxides; D001761:Bleomycin; D013936:Thymidine