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Exploiting the p-Bromodienone Route for the Formation and Trapping of Calixarene Oxenium Cations with Enamine
Annunziata Soriente1, Margherita De Rosa1, Pellegrino La Manna1
1Dipartimento di Chimica e Biologia "A. Zambelli" , Università di Salerno , Via Giovanni Paolo II 132 , Fisciano , Salerno I-84084 , Italy.
Abstract:
This study shows that calixarene p-bromodienone derivatives can act as precursors for the formation of oxenium cations, which can be trapped with enamine C-nucleophiles. When calixarene p-bromodienones were treated with enamines, in the presence of AgClO4, the lower rim-substituted C-O-C products were obtained by an electrophilic attack of the intermediate calixarene-oxenium cation with a contemporary cone-to-partial-cone inversion of the involved aromatic ring.
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In 1896, the German chemist Paul Walden discovered that he could interconvert pure enantiomeric (+) and (-) malic acids through a series of reactions. This conversion suggested the involvement of optical inversion during the substitution reaction. Further, in 1930, Sir Christopher Ingold described for the first time two different forms of nucleophilic substitution reactions, which are known as SN1 (nucleophilic substitution unimolecular) and SN2 (nucleophilic substitution...