title: Gosteli-Claisen rearrangement: substrate synthesis, simple diastereoselectivity, and kinetic studies.
abstract: The results of kinetic studies on the uncatalyzed [3,3]-sigmatropic rearrangement of 2-alkoxycarbonyl-substituted allyl vinyl ethers are reported. Apparently first reported by Gosteli in 1972, this variation of a Claisen rearrangement enjoyed a shadowy existence for three decades until its potential for the development of a catalytic asymmetric Claisen rearrangement was discovered. Inspired by this development, we have studied substituent and solvent rate effects, and we provide evidence that a chairlike transition state is highly favorable for the uncatalyzed Gosteli-Claisen rearrangement.
authors.affiliation: Fakultät Chemie, Technische Universität Dortmund, Germany. julia.rehbein@udo.edu
authors.forename: Julia
authors.initials: J
authors.lastname: Rehbein
authors.forename: Sabine
authors.initials: S
authors.lastname: Leick
authors.forename: Martin
authors.initials: M
authors.lastname: Hiersemann