The sigmatropic rearrangement of bicyclo[3.2.0]hept-2-ene to bicyclo[2.2.1]hept-1-ene has been studied both experimentally and theoretically for almost 50 years. The study of 7-methylbicyclo[3.2.0]hept-2-ene showed that the addition of an alkyl chain has a considerable impact on the reaction pathways and was long thought to be representative of the effect of all alkyl chains. We have expanded the study to five additional alkyl groups; ethyl, propyl, isopropyl, butyl, and <i>tert</i>-butyl in order to determine the effects of mass and steric hindrance on the rate of the sigmatropic rearrangement. Our results show that the rate and stereoselectivity of rearrangement is similar among all systems but that fragmentation becomes more competitive with isomerization as the mass of the alkyl group increases.

Thermal chemistry of 7-alkybicyclo[3.2.0]hept-2-enes

255th National Meeting (2018)

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