Rate constants for overall decomposition (kd) for a series of exo‐7‐alkylbicyclo[3.2.0]hept‐2‐enes are relatively invariant. For the alkyl substituents ethyl, propyl, butyl, isopropyl, and t‐butyl, the ratio of the rate constant for [1,3] sigmatropic rearrangement to the rate constant for fragmentation, k13/kf, is significantly lower than k13/kf = 150 observed for exo‐7‐methylbicyclo[3.2.0]hept‐2‐ene. Regardless of the size and mass of the alkyl group, the stereoselectivity of the [1,3] carbon migration appears to be quite stable at 80% to 89% suprafacial inversion (si), an observation consistent with conservation of angular momentum but not conservation of orbital symmetry. This global result comports with the phenomenon of “dynamic matching” espoused by Carpenter and collaborators for [1,3] sigmatropic rearrangements in general.
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