title: Computational and ¹³C investigations of the diazadienes and oxazadienes formed via the rearrangement of methylenecyclopropyl hydrazones and oximes.
abstract: Computational and further experimental investigations of the previously reported diazadienes, obtained via the rearrangement of methylenecyclopropyl hydrazone 1 are reported. Calculations at the CCSD(T)/cc-pVTZ//B3LYP/6-31G(d) level of theory indicate that the initially reported product 3 would, if formed, undergo rapid electrocyclic ring opening and, hence, would be unstable under the reaction conditions. Based on this computational prediction, further analysis of the (13)C NMR spectrum, previously attributed to 3, led to the revision of structure 3 to that of its N-tosylaminopyrrole constitutional isomer 11. Similarly, structure 8, formed in the rearrangement of oxime 6, was revised to that of N-hydroxypyrrole 12.
authors.affiliation: Department of Chemistry and Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas , 1155 Union Circle, #305070, Denton, Texas 76203-5070, United States.
authors.forename: Bo
authors.initials: B
authors.lastname: Chen
authors.forename: Mark E
authors.initials: ME
authors.lastname: Scott
authors.forename: Bruce A
authors.initials: BA
authors.lastname: Adams
authors.forename: David A
authors.initials: DA
authors.lastname: Hrovat
authors.forename: Weston Thatcher
authors.initials: WT
authors.lastname: Borden
authors.forename: Mark
authors.initials: M
authors.lastname: Lautens
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001372:Aza Compounds / Q000737:chemistry*; D006835:Hydrazones / Q000737:chemistry*; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010091:Oximes / Q000737:chemistry*; D011758:Pyrroles / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D000475:Alkenes; D001372:Aza Compounds; D006835:Hydrazones; D010091:Oximes; D011758:Pyrroles