Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5228664 | Tetrahedron | 2007 | 8 Pages |
A theoretical study of the 'walk' rearrangement in bicyclo[2.1.0]pentene and perfluorotetramethyl (Dewar thiophene) exo-S-oxide has been carried out. Despite the differences between them, the results for both reactions show an enhancement of aromaticity in the transition state, which is consistent with a pericyclic behavior. NBO calculations show that the small activation energy for the second reaction can be interpreted in terms of a strong stabilization of the transition state by the exo-oxide substituent. So, the mechanism proposed in the past should be revised.
Graphical abstractDownload full-size imageThe mechanism of this walk rearrangement was theoretically studied. The definition of pseudopericyclic reaction was based on the experimental behavior of this compound, which undergoes an extraordinarily facile automerization.