Register      Login
Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Unimolecular Rearrangements and Fragmentations in the Gas Phase: [1,3] Sigmatropic Isomerizations and [2 + 2] Cycloreversions

Mohammad R. Ahmad and Steven R. Kass

Australian Journal of Chemistry 56(5) 453 - 458
Published: 20 May 2003

Abstract

Trimethylsilyl ethers of 3-buten-2-ol, 1-vinylcyclopropanol, 1-vinylcyclobutanol, and cyclobutanol were treated with fluoride over a wide temperature range (–40 to 300°C) in a variable-temperature flowing afterglow–triple quadrupole device. The structures of the resulting alkoxides and enolates were probed by ion–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.

https://doi.org/10.1071/CH03002

© CSIRO 2003

Committee on Publication Ethics


Export Citation Get Permission

View Dimensions