Anwendung der NMR-Spektroskopie chiraler Assoziate 5: Chirale Butadiene 7: Stereodynamics and Diastereotopism in Chiral 1,3-Dienes HOCMe₂-(-CC1=CC1-)-₂R

Abstract

The barriers to partial rotation around the central single bond in chiral dienes HOCMe₂-(-CC1=CC1-)-₂R have been determined by coalescence of either 1H NMR signals (X = CH2OCH3) or 13C NMR signals (X = H). In the presence of the optically active shift reagent (+) − Eu(hfbc)3 all 1H signals were split at temperatures where the interconversion of enantiomers is slow. The temperature dependence of these spectra also yielded free activation enthalpies for the enantiomerizations which were in agreement with the ones obtained without Eu(hfbc)3. The assignment of the four methyl resonances appearing in the presence of (+) − Eu(hfbc)3 at low temperature was possible by gradually increasing the rate of enantiomerization or gradually replacing the optically active auxiliary compound by the racemic one.