RT Book,_Section
T1 Theoretical study of the pericyclic/pseudopericyclic character of the automerization of Perfluorotetramethyl (Dewar thiophene) exo-S-oxide
A1 Rodríguez Otero, Jesús
A1 Cabaleiro Lago, Enrique Manuel
A1 Peña Gallego, María de los Ángeles
AB A theoretical study of the "walk" rearrangement in bicyclo[2.1.0]pentene and perfluorotetramethyl (Dewar thiophene) exo-S-oxide has been carried out. In order to analyze the pericyclic character of these two reactions, some magnetic properties (NICS and ACID) have been calculated in the reactant/product and in the transition state of each reaction. 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 strongly stabilization of the transition state by the exo-oxide substituent. No evidence of any pseudopericyclic character has been found. Although the walk rearrangement in erfluorotetramethyl (Dewar thiophene) exo-S-oxide has special characteristics, the process of [1,3]-sigmatropic shift remains with a fundamental role in its mechanism. So, the mechanism proposed by Lemal et al, should be revised
PB MDPI
SN 3-906980-18-9
YR 2006
FD 2006
LK http://hdl.handle.net/10347/26820
UL http://hdl.handle.net/10347/26820
LA eng
NO Rodríguez-Otero, J.; Cabaleiro-Lago, E.M.; Peña-Gallego, A. Theoretical study of the pericyclic/pseudopericyclic character of the automerization of Perfluorotetramethyl (Dewar thiophene) exo-S-oxide, in Proceedings of the 10th International Electronic Conference on Synthetic Organic Chemistry, 1–30 November 2006, MDPI: Basel, Switzerland, doi:10.3390/ecsoc-10-01456
NO The 10th International Electronic Conference on Synthetic Organic Chemistry session Computational Chemistry
DS Minerva
RD 28 abr 2026