title: Effect of intramolecular Paternò-Büchi reaction on the thermodynamics and kinetics of nearly degenerate [3,3]-sigmatropic shift in fluxional polycycles.
abstract: In reactions with weak dienophiles, cyclooctatetraene (COT) often yields 2:1 adducts possessing the fluxional bicyclo[5.1.0]octadiene moiety. They undergo fast, nearly degenerate Cope rearrangement with an activation barrier similar to that of the parent dihydrobullvalene. Irradiation to excite the carbonyl moiety induces an intramolecular Paterno-Buchi cyclization yielding endo-oxetanes and significantly changing the Cope-averaged NMR spectra. In this paper we examine the effect of skeletal distortion caused by intramolecular [2 + 2]-photoaddition on thermodynamics and the activation barrier of the [3,3]-sigmatropic tautomerism. Our finding is that such a distortion lifts the energetic degeneracy of the two valence tautomers, while not affecting the activation barrier.
authors.affiliation: Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80208, USA.
authors.forename: Roman A
authors.initials: RA
authors.lastname: Valiulin
authors.forename: Donald G
authors.initials: DG
authors.lastname: Dressen
authors.forename: Jennifer R
authors.initials: JR
authors.lastname: Riggs
authors.forename: Faven M
authors.initials: FM
authors.lastname: Habte
authors.forename: Andrei G
authors.initials: AG
authors.lastname: Kutateladze