Effect of the α-Trifluoromethyl Moiety on the Solvolysis of Allylic Sulfonates

Article abstract of DOI:10.1021/jo00186a035

A series of allylic sulfonates bearing aryl substituents on the 2-position and/or trifluoromethyl groups on the 1- and/or 3-positions has been studied under solvolytic conditions in 2,2,2-trifluoroethanol.Nonarylated 1,3-di(trifluoromethyl)-substituted allylic sulfonates did not solvolyze in a conventional manner but instead gave products diagnostic of a complex isomerization-cleavage process.Mono(trifluoromethyl)-substituted allylic sulfonates solvolyzed by normal paths to give k_H/k_CF3 ratios of 2E6 and 4E4 for the substitution at the 1- and 3-positions, respectively.No evidence for 1,3-? interactions was discerned.