A DFT study of the Boulton-Katritzky rearrangement of (5R)-4-nitrosobenz[c]isoxazole and its anion: pseudopericyclic reactions with aromatic transition states

Angeles Peña-Gallego; Jesús Rodríguez-Otero; Enrique M Cabaleiro-Lago

doi:10.1021/jo0491509

A DFT study of the Boulton-Katritzky rearrangement of (5R)-4-nitrosobenz[c]isoxazole and its anion: pseudopericyclic reactions with aromatic transition states

J Org Chem. 2004 Oct 15;69(21):7013-7. doi: 10.1021/jo0491509.

Authors

Angeles Peña-Gallego¹, Jesús Rodríguez-Otero, Enrique M Cabaleiro-Lago

Affiliation

¹ Departamento de Química Física, Facultade de Química, Universidade de Santiago de Compostela, Avda das Ciencias s/n. 15782, Santiago de Compostela, Spain.

PMID: 15471446
DOI: 10.1021/jo0491509

Abstract

The nature of the Boulton-Katritzky rearrangement of (5R)-4-nitrosobenz[c]isoxazole and its anion was studied employing three methodologies: calculation of magnetic properties (magnetic susceptibility, magnetic susceptibility anisotropy, and the nucleus-independent chemical shifts), the natural bonding orbital analysis, and the ACID (anisotropy of the current-induced density) method. The deep analysis of the results indicates a pseudopericyclic character for these reactions despite the aromaticity of the transition states.