Please use this identifier to cite or link to this item: http://hdl.handle.net/10662/24539
Title: A fully diastereoselective oxidation of a mesoionic dipole with triplet molecular oxygen
Authors: García de la Concepción, Juan
Ávalos González, Martín
Jiménez Requejo, José Luis
Cintas Moreno, Pedro
Light, Mark E.
Keywords: Organic Chemistry;Physical and Theoretical Chemistry;Biochemistry;Química orgánica;Química Física y Teórica;Bioquímica
Issue Date: 2020
Publisher: Royal Society of Chemistry
Abstract: Oxidations with molecular oxygen are ubiquitous processes in biological systems where cofactordependent enzymes activate either oxygen or hydrogen peroxide to induce multichannel pathways. In stark contrast, such slow atmospheric oxidations are seldom harnessed in chemical synthesis and analysis. The present study unveils an unusual aerobic oxidation of a mesoionic dipole leading easily to a more functionalized skeleton. Although the synthetic scope has not been explored, two key considerations emerge from this transformation, as it proceeds with complete diastereoselection and could be successfully extrapolated to structurally related mesoionic chirons without racemization. How this oxidation actually occurs proved to be puzzling from the onset and only high-level computation reveals a cascade transformation, whose results reconcile theory and experiment. Hopefully, the mechanistic insights should help us to understand better the autoxidative reactions of organic molecules.
URI: http://hdl.handle.net/10662/24539
ISSN: 1477-0520
DOI: 10.1039/d0ob01428a
Appears in Collections:DQOIN - Artículos

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