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        Intramolecular cyclization of β-nitroso-o-quinone methides : A theoretical endoscopy of a potentially useful innate 'reclusive' reaction

        Author
        Tzeli, Demeter
        Tsoungas, Petros G.
        Petsalakis, Ioannis D.
        Kozielewicz, Paweł
        Zloh, Mire
        Attention
        2299/15229
        Abstract
        Oxidatively generated β-nitroso-o-quinone methides undergo an o- and/or peri-intramolecular cyclization to arene-fused 1,2-oxazoles, 1,2-oxazines or indoles. The reaction, found to be an innate process, has been scrutinized by DFT/B3LYP and MP2 calculations. Due to its rapidity, the process has been termed a 'reclusive' one. Competing o-(1,5)- and peri-(1,6)- or (1,5)-cyclizations advance via successive transition states. Activation barriers are drastically lowered in AcOH, probably through H hopping or tunnelling whereas they are barely reduced in other solvents. Aromaticity indices, such as HOMA, IA and ABO, have been used to assess the stability of the end-heterocycles and the preponderance of any one of them. Thus, the preferred cyclization mode, that is, the prevalence or exclusive formation of one of the heterocycles, appears to be oxidant-directed rather than determined by the quinone methide geometry. The question of the peri-cyclization, being a primary or a secondary process, has been tackled.
        Publication date
        2015-01-14
        Published in
        Tetrahedron
        Published version
        https://doi.org/10.1016/j.tet.2014.11.020
        Other links
        http://hdl.handle.net/2299/15229
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