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Theoretical insights into the mechanism of copper-catalyzed cyclopropanation reaction of 2-butene

AutorHormigón, Z.; Angulo, Beatriz; Mayoral, José A. ; Salvatella, Luis
Fecha de publicación2016
CitaciónESPA 2016
ResumenThe mechanism of the copper(I)-catalyzed cyclopropanation reaction for 2-butene has been studied by means of M06-2X/6-311++G(d,p) calculations. The rate-limiting step is the formation of a copper-carbene intermediate (formed by association of methyl diazoacetate and the catalyst with concomitant extrusion of nitrogen; ΔE = 96.6 kJ/mol), with an activation barrier of the overall process of 203.6 kJ/mol. These high barriers are due to the chosen catalyst model (tetrakis(acetonitrile)copper(I)), which probably does not exist and is more stable than the real catalytic specie under the reaction conditions, leading to an overestimation of these activation energies. Assuming a concerted mechanism for the formation of the cyclopropane ring (i.e. direct carbene insertion), based on previous studies, selectivity cis/trans will be discussed by comparison of the relative energies of the transition structures for cis-2-butene.
DescripciónResumen del póster presentado al 10th Congress on Electron Strucuture: Principles and Apllications, celebrado en Castellón de la Plana (España) del 28 de junio al 1 de julio de 2016.
URIhttp://hdl.handle.net/10261/156132
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