
%0 Journal Article
%A Ahmad, Mohammad R. 
%A Kass, Steven R. 
%T Unimolecular Rearrangements and Fragmentations in the Gas Phase: [1,3] Sigmatropic Isomerizations and [2 + 2] Cycloreversions
%J Australian Journal of Chemistry
%D 2003/05/23
%V 56
%N 5
%P 453-458
%K 
%R https://doi.org/10.1071/CH03002
%U https://www.publish.csiro.au/paper/CH03002 
%X Trimethylsilyl ethers of 3-buten-2-ol, 1-vinylcyclopropanol, 1-vinylcyclobutanol, and cyclobutanol were treated with fluoride over a wide temperature range (&#8211;40 to 300&#176;C) in a variable-temperature flowing afterglow&#8211;triple quadrupole device. The structures of the resulting alkoxides and enolates were probed by ion&#8211;molecule reactions and their collision-induced dissociation (CID) spectra. Activation energies were obtained for several anion-accelerated [1,3] sigmatropic rearrangements and [2 + 2] cycloreversions. The mechanisms for these isomerizations and fragmentations (stepwise versus concerted) and their synthetic potential are discussed. 
