
TY  - JOUR
A1  - Ahmad, Mohammad R. 
A1  - Kass, Steven R. 
T1  - Unimolecular Rearrangements and Fragmentations in the Gas Phase: [1,3] Sigmatropic Isomerizations and [2 + 2] Cycloreversions
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 2003
VL  - 56
IS  - 5
SP  - 453
EP  - 458
KW  - 
UR  - https://doi.org/10.1071/CH03002 
N2  - 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. 
ER  -

