title: Computational explorations of vinylcyclopropane-cyclopentene rearrangements and competing diradical stereoisomerizations
abstract: The rearrangements and stereoisomerizations of four systems, vinylcyclopropane, 4-tert-butylvinylcyclopropane, 5-methylvinylcyclopropane, and 2,5-dimethylvinylcyclopropane, as well as a variety of deuterated derivatives and 1- and 2-methyl-, methoxy-, difluoro-, and amino-substituted species, were studied by density functional theory calculations using the B3LYP functional and the 6-31G basis set. Energies were evaluated with CASSCF(4, 4)/6-31G single point calculations. The major product is obtained by the si pathway. Structures on this path are essentially pure diradical in character. Higher energy diradical species and intermediates are responsible for the scrambling of the stereochemistry. The stereoselectivity of the reaction is increased by substituents which increase the relative energy of the species involved in competing stereoselectivities. The computed secondary kinetic isotope effects reproduce the experimental values reported in the literature.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569 and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556-5670, USA.
authors.initials: M
authors.lastname: Nendel
authors.initials: D
authors.lastname: Sperling
authors.initials: O
authors.lastname: Wiest
authors.initials: KN
authors.lastname: Houk