Understanding Experimental Facts for the Transformation of Perezone into α- and β-pipitzols

Under thermal conditions perezone, a sesquiterpene quinone, forms an equimolar amount of a- and β-pipitzol through an intermolecular cycloaddition reaction. Computational calculations at M06-2x/6-311++G(2d,2p) level of theory of the transition states and the associated reaction paths allow justifyin...

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Published in:Journal of the Mexican Chemical Society 2024-01, Vol.68 (1), p.88-98
Main Authors: Soto Suárez, Fatima Montserrat, Cuevas González Bravo, Gabriel Eduardo, Murillo Herrera, Luis Mauricio, Hernández-Huerta, Eduardo, Ortiz Reynoso, Mariana, Ramírez Gualito, Karla, Quijano Quiñones, Ramiro Felipe
Format: Article
Language:English
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Summary:Under thermal conditions perezone, a sesquiterpene quinone, forms an equimolar amount of a- and β-pipitzol through an intermolecular cycloaddition reaction. Computational calculations at M06-2x/6-311++G(2d,2p) level of theory of the transition states and the associated reaction paths allow justifying the experimental observations. Only exo adducts are observed experimentally, which is in line with the calculated energy difference of 6.5 kcal/mol between the transition states associated with the endo and exo adducts. Activation free energy was accurately predicted, those the uncatalyzed thermal process of cycloaddition requires 37.0 kcal/mol. The study of the potential energy surface allows to establish the existence of folded conformers of perezone in the potential energy surface.   Resumen. En condiciones térmicas la perezona, una quinona sesquiterpénica, forma, cantidades equimolares de a- y β-pipitzoles a través de una reacción de cicloadición intramolecular. A nivel M06-2x/6-311++G(2d,2p) el cálculo de los estados de transición y de las trayectorias de reacción asociadas permiten justificar los resultados observados. Desde el punto de vista experimental sólo se forman los aductos exo y no los endo pues los estados de transición relacionados muestran una diferencia energética de 6.5 kcal/mol. La energía de activación calculada para el procedo desprovisto de catálisis es de 37.0 kcal/mol. El estudio de la superficie de energía potencial permite establecer la existencia de confórmeros plegados de la perezona.
ISSN:1870-249X
2594-0317
DOI:10.29356/jmcs.v68i1.1926