Abstract: Rearrangement rates for nineteen Qallyl silylketene acetals {[(I-(allyloxy)-1-ethenyl) oxy] trialkylsilanes) are reported. Whereas rates for rearrangement of 1 and 2 exhibit a linear free energy relationship, no linear free energy relationship is observed between rates for 1 and 3. These data suggest the possibility of “syn-diaxial” interactions in a chair-like transition state for rearrangements of 3. The difference in free energy between 2 and 3 is found to be ...
