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Environmental effects on Cu(II)-catalyzed hetero-Diels–Alder reactions: computational approach

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Abstract

The efficiency of transition metal-catalyzed reactions critically depends on the chemical environment. This investigation addresses the role of the counterions and solvent molecules on the transition states and energetics of Cu(II)-catalyzed hetero-Diels–Alder reactions (the addition of ethyl glyoxylate to cyclopentadiene) by theoretical calculations. Ethylenediamine was used as a model ligand to systematically assess the effects caused by the counterions OTf−, BF4 −, PF6 −, Cl−, and SbF6 − and the solvents CH2Cl2, CHCl3, CH3NO2, and CH3CN. It is shown how the energies of the transition states, the geometry of the Cu(II) complexes formed in the course of the catalytic reactions, and the asynchronicity of the C–C bond-forming reaction are changed by the presence of solvent molecules and counterions. Our computational results indicate the mechanistic background of experimental results and provide perspectives for an efficient choice of reaction conditions.

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Acknowledgments

This work was supported by FWF (Austria), Project No. P23847.

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Authors and Affiliations

  1. Institute of Physical and Theoretical Chemistry, Graz University of Technology, Stremayrgasse 9, 8010, Graz, Austria

    Pawel Cias & Georg Gescheidt

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  1. Pawel Cias
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  2. Georg Gescheidt
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Correspondence to Pawel Cias.

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Cias, P., Gescheidt, G. Environmental effects on Cu(II)-catalyzed hetero-Diels–Alder reactions: computational approach. Monatsh Chem 146, 1267–1274 (2015). https://doi.org/10.1007/s00706-015-1510-z

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  • DOI: https://doi.org/10.1007/s00706-015-1510-z

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