title: Ab initio calculations on (-)-calicheamicinone and some of its reactions involved in its activation and interaction with DNA.
abstract: Ab initio calculations were performed on (-)-calicheamicinone, and on the product (Z or E) of the Michael addition via a reaction with methanethiol. It is found that the sulfur moiety position versus the rest of the molecule is quite flexible. The Michael adduct featuring the carbamate group E to the sulfur moiety is more stable than the Z isomer. The Bergman reaction of the diradical formation is strongly exothermic.
authors.affiliation: City University of New York, John Jay College and Graduate School, New York 10019, USA.
authors.forename: R
authors.initials: R
authors.lastname: Rothchild
authors.forename: A M
authors.initials: AM
authors.lastname: Sapse
authors.forename: A
authors.initials: A
authors.lastname: Balkova
authors.forename: J W
authors.initials: JW
authors.lastname: Lown
mesh_terms: D000617:Aminoglycosides; D000900:Anti-Bacterial Agents / Q000737:chemistry* / Q000378:metabolism* / Q000494:pharmacology; D000903:Antibiotics, Antineoplastic / Q000737:chemistry* / Q000378:metabolism* / Q000494:pharmacology; D004247:DNA / Q000187:drug effects / Q000378:metabolism*; D004355:Drug Stability; D053281:Enediynes; D066298:In Vitro Techniques; D008956:Models, Chemical; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D000617:Aminoglycosides; D000900:Anti-Bacterial Agents; D000903:Antibiotics, Antineoplastic; D053281:Enediynes; C055955:calicheamicin gamma(1)I; D004247:DNA