ACTIVATION OF FE(III).BLEOMYCIN BY 10-HYDROPEROXY-8,12-OCTADECADIENOIC ACID

Treatment of 10-hydroperoxy-8,12 octadecadienoic acid with Fe(III)-bleomycin (BLM) resulted in reduction of the hydroperoxide to afford 10-oxo-8-decenoic acid, which must form by homolytic scission of the peroxide O-O bond. Although this reaction afforded a reactive species that could demethylate A.N-dimethylaniline and convert styrene to styrene oxide and phenylacetaldehyde, the extent of conversion was much less than that obtained following activation of Fe(III)-BLM with hydrogen peroxide. Further, unlike the activated species formed by admixture of Fe(III)-BLM + H2O2 or ethyl hydroperoxide, the activated Fe-BLM formed via the agency of 10-hydroperoxy-8,12-octadecadienoic acid would not mediate the destruction of the self-complementary oligonucleotide 5’-d(CGCT3A3GCG), nor would it support naphthalene hydroxylation. These results suggest that the activated Fe-BLM formed from Fe(III)-BLM + H2O2 may differ from the species generated when Fe(III)-BLM reacts with alkyl peroxides that undergo homolytic O-O bond scission. © 1990, American Chemical Society. All rights reserved.