[1,3]-Sigmatropic Rearrangements
The Vinylcyclopropane-Cyclopentene Rearrangement,
T. Hudlicky, T. M. Kutchan, S. M. Naqvi, Org. React. 1985, 33, 247.
Vinylcyclopropane Rearrangements,
Z. Goldschmidt, B. Crammer, Chem. Soc. Rev. 1988, 17, 229.
Thermal [1,3] Carbon Sigmatropic Rearrangements of Vinylcyclobutanes,
Leber, P. A.; Baldwin, J. E. Acc. Chem. Res. 2002, 35, 279-87.
Thermal Rearrangements of Vinyl-cyclopropanes to Cyclopentenes,
Baldwin, J. E. Chem Rev. 2003, 103, 1197-212.
The suprafacial [1,3]-sigmatropic rearrangement is an orbital symmetry forbidden process, and thus typically has high activation barriers and potentially proceeds through radical or zwitterionic intermediates. Such rearrangements can, however be performed in special circumstances where ring strain lowers the activation barrier, for example in vinyl cyclopropanes.
Vinyl cyclopropane rearrangement
Hirsutene: Hudlicky, T.; Kutchan, T. M.; Wilson, S. R.; Mao, D. T. J. Am. Chem. Soc. 1980, 102, 6351. DOI
