000130656 001__ 130656 000130656 005__ 20240130150402.0 000130656 0247_ $$2doi$$a10.1007/s00894-018-3737-1 000130656 0248_ $$2sideral$$a107064 000130656 037__ $$aART-2018-107064 000130656 041__ $$aeng 000130656 100__ $$aAngulo, B. 000130656 245__ $$aCopper-catalyzed cyclopropanation reaction of but-2-ene 000130656 260__ $$c2018 000130656 5060_ $$aAccess copy available to the general public$$fUnrestricted 000130656 5203_ $$aThe 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. 000130656 536__ $$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52367-R 000130656 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/ 000130656 590__ $$a1.335$$b2018 000130656 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b122 / 172 = 0.709$$c2018$$dQ3$$eT3 000130656 591__ $$aCOMPUTER SCIENCE, INTERDISCIPLINARY APPLICATIONS$$b85 / 106 = 0.802$$c2018$$dQ4$$eT3 000130656 591__ $$aBIOCHEMISTRY & MOLECULAR BIOLOGY$$b262 / 294 = 0.891$$c2018$$dQ4$$eT3 000130656 591__ $$aBIOPHYSICS$$b59 / 72 = 0.819$$c2018$$dQ4$$eT3 000130656 592__ $$a0.37$$b2018 000130656 593__ $$aCatalysis$$c2018$$dQ3 000130656 593__ $$aComputational Theory and Mathematics$$c2018$$dQ3 000130656 593__ $$aPhysical and Theoretical Chemistry$$c2018$$dQ3 000130656 593__ $$aInorganic Chemistry$$c2018$$dQ3 000130656 593__ $$aOrganic Chemistry$$c2018$$dQ3 000130656 593__ $$aComputer Science Applications$$c2018$$dQ3 000130656 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion 000130656 700__ $$0(orcid)0000-0002-7272-8506$$aHerrerías, C.I.$$uUniversidad de Zaragoza 000130656 700__ $$0(orcid)0000-0002-8805-4374$$aHormigón, Z.$$uUniversidad de Zaragoza 000130656 700__ $$0(orcid)0000-0003-1570-4257$$aMayoral, J.A.$$uUniversidad de Zaragoza 000130656 700__ $$0(orcid)0000-0003-2010-9540$$aSalvatella, L.$$uUniversidad de Zaragoza 000130656 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica 000130656 773__ $$g24 (2018), [8 pp]$$pJ. Mol. Model.$$tJOURNAL OF MOLECULAR MODELING$$x1610-2940 000130656 8564_ $$s630786$$uhttps://zaguan.unizar.es/record/130656/files/texto_completo.pdf$$yPostprint 000130656 8564_ $$s1567538$$uhttps://zaguan.unizar.es/record/130656/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint 000130656 909CO $$ooai:zaguan.unizar.es:130656$$particulos$$pdriver 000130656 951__ $$a2024-01-30-14:05:39 000130656 980__ $$aARTICLE