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Copper-catalyzed cyclopropanation reaction of but-2-ene

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Abstract

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.

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Acknowledgments

The Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) and the Instituto de Biocomputación y Física de Sistemas Complejos (BIFI) (Consejo Superior de Investigaciones Científicas (CSIC)–Universidad de Zaragoza) are thanked for the allocation of computer time. Financial support from Ministerio de Economía y Competitividad (MINECO) (Project CTQ2014-52367-R), Gobierno de Aragón, European Regional Development Fund (Consolidated Group E11), and European Social Fund is gratefully acknowledged.

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Authors and Affiliations

  1. Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC–Universidad de Zaragoza, Pedro Cerbuna 12, E-50009, Zaragoza, Spain

    Beatriz Angulo, Clara I. Herrerías, Zoel Hormigón, José Antonio Mayoral & Luis Salvatella

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  1. Beatriz Angulo
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  2. Clara I. Herrerías
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  3. Zoel Hormigón
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  4. José Antonio Mayoral
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  5. Luis Salvatella
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Correspondence to Luis Salvatella.

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Angulo, B., Herrerías, C.I., Hormigón, Z. et al. Copper-catalyzed cyclopropanation reaction of but-2-ene. J Mol Model 24, 195 (2018). https://doi.org/10.1007/s00894-018-3737-1

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