Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides

Exequiel O. J. Porta; Margarita M. Vallejos; Andrea B. J. Bracca; Guillermo R. Labadie

doi:10.1039/C7RA09759J

Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides†

Exequiel O. J. Porta,^a Margarita M. Vallejos,^b Andrea B. J. Bracca

^a and Guillermo R. Labadie

*^ac

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* Corresponding authors

^a Instituto de Química Rosario, UNR, CONICET, Suipacha 531, Rosario, Argentina
E-mail: labadie@iquir-conicet.gov.ar
Fax: +54-341-4370477 ext. 112
Tel: +54-341-4370477 ext. 108

^b Laboratorio de Química Orgánica, IQUIBA-NEA, Universidad Nacional del Nordeste, CONICET, FACENA, Av. Libertad 5460, Corrientes 3400, Argentina

^c Departamento de Química Orgánica, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario, Argentina

Abstract

[3,3]-Sigmatropic rearrangement of isoprenyl azides has been extensively investigated in an experimental and theoretical level. Prenylazides with different chain lengths and phenyl prenylazide have been synthesized. NMR analysis of each azide has been made to determine the equilibrium composition, showing the predominance of primary allyl azides over the tertiary ones and E over Z isomer, regardless of the chain length, temperature, solvent or the regiochemistry of the precursor isoprenyl alcohol. It was determined that phenyl prenylazides do not experience [3,3]-sigmatropic rearrangement. In order to rationalize the experimental results and to gain insight in the mechanism of the [3,3]-sigmatropic rearrangement of prenylazides a theoretical study was performed using density functional theory and the QTAIM approach.

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DOI: https://doi.org/10.1039/C7RA09759J
Article type: Paper
Submitted: 02 Sep 2017
Accepted: 03 Oct 2017
First published: 10 Oct 2017
This article is Open Access

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RSC Adv., 2017,7, 47527-47538

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Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides

E. O. J. Porta, M. M. Vallejos, A. B. J. Bracca and G. R. Labadie, RSC Adv., 2017, 7, 47527 DOI: 10.1039/C7RA09759J

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Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides†

Abstract

Supplementary files

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Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides

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