Studies on the mechanism of action of prekinamycin, a member of the diazoparaquinone family of natural products: evidence for both sp2 radical and orthoquinonemethide intermediates.
The putative reductive activation chemistry of the diazoparaquinone antibiotics was modeled with Bu(3)Sn-H and prekinamycin dimethyl ether along with prekinamycin itself. Reaction in various combinations of aromatic solvents, with and without the nucleophile benzylmercaptan present, led to isolation of both radical-trapping arene adducts and nucleophilic capture benzyl thioether products. On the basis of these product distribution studies, the intermediacies of, first, a cyclopentenyl radical and, next, an orthoquinonemethide electrophile are postulated.
Feldman
Ken S
KS
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA. ksf@chem.psu.edu
Eastman
Kyle J
KJ
D000890:Anti-Infective Agents / Q000737:chemistry* / Q000494:pharmacology; D011809:Quinones / Q000737:chemistry* / Q000494:pharmacology; D000095602:Angucyclines and Angucyclinones
D000890:Anti-Infective Agents; D011809:Quinones; C059018:pre-kinamycin; D000095602:Angucyclines and Angucyclinones