title: Thermal reaction of [3,4]-benzo-8-substituted-3Z,5Z,7E-octatetraenes and quantum-chemical study of the (8π,6π)-electrocyclisation.
abstract: The first example of thermal (8π,6π)-electrocyclisation of 1,3,5,7-octatetraene with one double bond embedded in an aromatic moiety is described. By this process, [3,4]-benzo-8-substituted octatetraene derivatives, the cis,trans-1-(o-vinylphenyl)-4-(R = Me, Ph, 2-furyl)buta-1,3-dienes were transformed to a new endo-7-(R = Me, Ph, 2-furyl) and exo-7-(R = Me)-2,3-benzobicyclo[4.2.0]octa-2,4-dienes. Mechanism of reaction was also studied by DFT quantum-chemical calculations. The M06/6-311+G(d,p)//M06/6-31+G(d,p) calculations indicate that formation of the single endo-isomer in the case of phenyl and 2-furyl substituents is determined by higher activation barriers for exo-6π-electrocyclisation than for 8π-cycloreversion.
authors.affiliation: Department of Organic Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, 10000, Zagreb, Croatia. iskoric@fkit.hr
authors.forename: Irena
authors.initials: I
authors.lastname: Škorić
authors.forename: Fabijan
authors.initials: F
authors.lastname: Pavošević
authors.forename: Mario
authors.initials: M
authors.lastname: Vazdar
authors.forename: Željko
authors.initials: Ž
authors.lastname: Marinić
authors.forename: Marija
authors.initials: M
authors.lastname: Šindler-Kulyk
authors.forename: Mirjana
authors.initials: M
authors.lastname: Eckert-Maksić
authors.forename: Davor
authors.initials: D
authors.lastname: Margetić
mesh_terms: D003500:Cyclization; D034242:Cyclooctanes / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism; D013696:Temperature
chemical_list: D034242:Cyclooctanes; C534209:1,3,5,7-cyclooctatetraene