Stereochemistry of the thermal isomerizations of (2S,3R-methoxymethyl-2,3-dideuterio-1-(dideuteriomethylene)cyclopropane

The (2S,3R) isomer of 2-methoxymethyl-2,3-dideuterio-1-(dideuteriomethylene)cyclopropane has been synthesized and heated at 198.8°: from the experimentally observed mol fractions of the eight isomers of 2,3,α,α,- and 2,3,3,α - tetradeuterio - 2 - methoxymethyl - 1 - methylenecyclopropane in the pyrolysis product mixture have been derived rate constants for seven distinct modes of isomerization. One-center thermal epimerizations at C(2) and C(3) and the C(2)C(3) two-center epimerization are of kinetic importance. Only two of four observable stereochemical modes for carbon [1,3] shifts are seen: there is inversion of stereochemistry at the migrating C atom, while the C(3)H trans to C(2)-CH₂OCH₃ in starting material becomes syn 4 : 1 C(α)-H in the [1,3] shift product. Stereomutation at C(2) does not occur along the reaction coordinate for [1,3] carbon shifts.