130656 20240130150402.0 doi 10.1007/s00894-018-3737-1 sideral 107064 ART-2018-107064 eng Angulo, B. Copper-catalyzed cyclopropanation reaction of but-2-ene 2018 The mechanism of the copper(I)-catalyzed cyclopropanation reaction for methyl diazoacetate with both (Z)- and (E)-but-2-ene stereoisomers has been studied using the 6-311++G(d, p) basis set by means of M06-2X and O3LYP functionals. According to both methods, the rate-limiting step is the formation of a copper-carbene intermediate, formed by association between methyl diazoacetate and bis(acetonitrile)-copper(I) ion with the concomitant extrusion of dinitrogen. Cis/trans diastereoselectivity for the cyclopropanation reaction of a 1, 2-disubstituted alkene ((Z)-but-2-ene) has been theoretically studied for the first time through the proper location of transition states on the potential-energy surface with the O3LYP method, since no transition structures could be found with the M06-2X functional due to the extreme flatness of the potential-energy surface. The calculated stereoselectivities involving two acetonitrile ligands or one dichloromethane molecule show qualitative agreement with experimental data. This study allows attributing the origin of the selectivity to steric interactions between the ligands of the catalyst system and the olefin substituents. The comparison between the corresponding activation barriers for the direct insertion step shows a higher reactivity for the Z stereoisomer of but-2-ene, consistently with the larger reactant destabilization through steric interactions. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52367-R info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 1.335 2018 CHEMISTRY, MULTIDISCIPLINARY 122 / 172 = 0.709 2018 Q3 T3 COMPUTER SCIENCE, INTERDISCIPLINARY APPLICATIONS 85 / 106 = 0.802 2018 Q4 T3 BIOCHEMISTRY & MOLECULAR BIOLOGY 262 / 294 = 0.891 2018 Q4 T3 BIOPHYSICS 59 / 72 = 0.819 2018 Q4 T3 0.37 2018 Catalysis 2018 Q3 Computational Theory and Mathematics 2018 Q3 Physical and Theoretical Chemistry 2018 Q3 Inorganic Chemistry 2018 Q3 Organic Chemistry 2018 Q3 Computer Science Applications 2018 Q3 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Herrerías, C.I. Universidad de Zaragoza (orcid)0000-0002-7272-8506 Hormigón, Z. Universidad de Zaragoza (orcid)0000-0002-8805-4374 Mayoral, J.A. Universidad de Zaragoza (orcid)0000-0003-1570-4257 Salvatella, L. Universidad de Zaragoza (orcid)0000-0003-2010-9540 2013 765 Universidad de Zaragoza Dpto. Química Orgánica Área Química Orgánica 24 (2018), [8 pp] J. Mol. Model. JOURNAL OF MOLECULAR MODELING 1610-2940 630786 http://zaguan.unizar.es/record/130656/files/texto_completo.pdf Postprint 1567538 http://zaguan.unizar.es/record/130656/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:130656 articulos driver 2024-01-30-14:05:39 ARTICLE