title: The Role of Strain in the Homoaromatization of Semibullvalenes.
abstract: The low activation barrier to the Cope rearrangement of semibullvalenes has been attributed to the inherent ring-strain of this nucleus. Appropriate, Dewar-Hoffmann, substitution of semibullvalene results in the stabilization of the transition state and a further lowering of the Cope barrier. An alternative proposal for lowering/eliminating this barrier is the use of strain to destabilize the localized semibullvalene. Using density functional and Hartree-Fock calculations, we predict that additionally straining the semibullvalene nucleus, by small ring annelations, will lead to a lowering of the Cope barrier and ultimately to ground state neutral homoaromatics.
authors.affiliation: Department of Chemistry, University of Idaho , 875 Perimeter Drive, Mail Stop 2343, Moscow, Idaho 83844-2343, United States.
authors.forename: Richard Vaughan
authors.identifier: 0000-0001-5935-3618
authors.initials: RV
authors.lastname: Williams
authors.affiliation: Department of Chemistry, University of Idaho , 875 Perimeter Drive, Mail Stop 2343, Moscow, Idaho 83844-2343, United States.
authors.forename: Abdullah G
authors.initials: AG
authors.lastname: Al-Sehemi
authors.affiliation: Department of Chemistry, University of Idaho , 875 Perimeter Drive, Mail Stop 2343, Moscow, Idaho 83844-2343, United States.
authors.forename: Amanda K
authors.initials: AK
authors.lastname: Meier
authors.affiliation: Department of Chemistry, University of Idaho , 875 Perimeter Drive, Mail Stop 2343, Moscow, Idaho 83844-2343, United States.
authors.forename: Zachary Z
authors.initials: ZZ
authors.lastname: Brown
authors.affiliation: Department of Chemistry, University of Idaho , 875 Perimeter Drive, Mail Stop 2343, Moscow, Idaho 83844-2343, United States.
authors.forename: John R
authors.initials: JR
authors.lastname: Armantrout