ChemInform Abstract: Kinetic and Stereochemical Effect of a Fluorine Substituent on the Cope and the Homodienyl 1,5-Hydrogen Shift Rearrangements.

ChemInform Abstract

The kinetics and stereochemical outcome for the thermal rearrangements of the 3-fluorohexadiene (II) and the 1-cis-fluoromethyl-2-vinylcyclopropane (XIIa) are investigated. The relative proportions of the Z and E products (III)/(IV) and (XIII)/(XIV), resp., in each case reflect their relative stability, thus indicating the lack of any dramatic kinetic effects due to the presence of the fluorine substituents in contrast to the very dramatic effects observed in cyclobutene-butadiene interconversions. The reactants (II) and (XII), and the products (III) and (IV) are prepared as given in the scheme.