Abstract
In an explorative study of the opportunities for synthesis provided by oxidation of natural aminoacidic compound with methyl-(trifluoromethyl)dioxirane, we noticed that oxidation of the cyclic compound, when successful, leads to the ?-hydroxy compound, notwithstanding the presence of the isopropyl groups that are usually easy targets for this reaction, as verified with the homologous acyclic compound. We therefore initiated an ab-initio study of the reactions aimed at determining the role of the ring and explaining the reactivity differences of the cis and trans configurations. Consistently with recent literature, we confirm the fundamental role of an adduct configuration in which the dioxirane O-O bond is largely divaricated and electron pairing is broken, often denoted in the literature as diradicaloid.
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Acknowledgments
The research was supported by CNR ICCOM and Regione Puglia MIUR PON Ricerca e Competitività 20072013 Avviso 254/Ric. del 18/05/2011, Project PONa3 00369 Laboratorio SISTEMA.
Commercial Caroat® triple salt (\(\mathrm {2 KHSO_5 \cdot KHSO_4 \cdot K_2SO_4}\)) was kindly supplied by Peroxide-Chemie, (Degussa, Germany).
We acknowledge the CINECA award under the ISCRA initiative, class C, project dichetox, for the availability of high performance computing resources and support.
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Annese, C., D’Accolti, L., Fusco, C., Ciriaco, F. (2016). Ab-initio Investigation of Unexpected Aspects of Hydroxylation of Diketopiperazines by Reaction with Dioxiranes. In: Rossi, F., Mavelli, F., Stano, P., Caivano, D. (eds) Advances in Artificial Life, Evolutionary Computation and Systems Chemistry. WIVACE 2015. Communications in Computer and Information Science, vol 587. Springer, Cham. https://doi.org/10.1007/978-3-319-32695-5_13
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DOI: https://doi.org/10.1007/978-3-319-32695-5_13
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