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Type: Artigo de periódico
Title: Regioselectivity in aromatic Claisen rearrangements
Author: Gozzo, FC
Fernandes, SA
Rodrigues, DC
Eberlin, MN
Marsaioli, AJ
Abstract: Theoretical calculations and the isomeric product composition for a series of eight meta-substituted allyl aryl ethers confirm the reliability of a new H-1 NMR methodology used to predict aromatic Claisen regioselectivity from ground-state conformational preference of the reactant allyloxy group. Frontier HOMO-LUMO intramolecular orbital interactions, a classical approach in predicting reactivity and selectivity for Claisen rearrangements of allyl vinyl ethers, is shown to fail to mimic transition-state orbital interactions for aromatic Claisen rearrangements of meta-substituted allyl aryl ethers. B3LYP/6-31G(d,p) calculations on reactants and transition states are shown, however, to correctly predict the outcome of such aromatic Claisen rearrangements from either the preferential reactant ground-state conformation (theoretical predictions that agree with the NMR measurements) or the less energetic transition state, or both.
Country: EUA
Editor: Amer Chemical Soc
Citation: Journal Of Organic Chemistry. Amer Chemical Soc, v. 68, n. 14, n. 5493, n. 5499, 2003.
Rights: fechado
Identifier DOI: 10.1021/jo026385g
Date Issue: 2003
Appears in Collections:Unicamp - Artigos e Outros Documentos

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