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Issue 17, 2011
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Sigmatropic rearrangements in 5-allyloxytetrazoles

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Abstract

Mechanisms of thermal isomerization of allyl tetrazolyl ethers derived from the carbocyclic allylic alcohols cyclohex-2-enol and 3-methylcyclohex-2-enol and from the natural terpene alcohol nerol were investigated. In the process of the syntheses of the three 1-aryl-5-allyloxytetrazoles, their rapid isomerization to the corresponding 1-aryl-4-allyltetrazol-5-ones occurred. The experiments showed that the imidates rearrange exclusively through a [3,3′]-sigmatropic migration of the allylic system from O to N, with inversion. Mechanistic proposals are based on product analysis and extensive quantum chemical calculations at the DFT(B3LYP) and MP2 levels, on O-allyl and N-allyl isomers and on putative transition state structures for [1,3′]- and [3,3′]-sigmatropic migrations. The experimental observations could be only explained on the basis of the MP2/6-31G(d,p) calculations that favoured the [3,3′]-sigmatropic migrations, yielding lower energies both for the transition states and for the final isomerization products.

Graphical abstract: Sigmatropic rearrangements in 5-allyloxytetrazoles

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Article information


Submitted
22 Mar 2011
Accepted
23 May 2011
First published
24 May 2011

Org. Biomol. Chem., 2011,9, 6040-6054
Article type
Paper

Sigmatropic rearrangements in 5-allyloxytetrazoles

L. M. T. Frija, I. Reva, A. Ismael, D. V. Coelho, R. Fausto and M. L. S. Cristiano, Org. Biomol. Chem., 2011, 9, 6040
DOI: 10.1039/C1OB05460K

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