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Understanding the high reactivity of triazolinediones in Diels-Alder reactions. A DFT study

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Abstract

The participation of 4-substituted-1,2,4-triazoline-3,5-diones (TADs) in Diels-Alder reactions toward a series of dienes is studied at the M05-2X/6-31+G(d,p) level. These reactions show very low activation energies and complete endo selectivity, in agreement with the experimental data. For a dienic steroid model, the reaction presents an α-facial selectivity. Analysis of reactivity indices explains the superelectrophilic character of TADs, and low activation energy. The substituent and solvent effects are also evaluated.

The Diels-Alder reactions between 4-substituted-1,2,4-triazoline-3,5-diones (TADs) and a series of dienes are studied by DFT computations at the M05-2X/6-31+G(d,p) level. Our computations support a series of features listed as follows: 1) low activation energies, 2) complete endo selectivity, 3) the superelectrophilic character of TADs, 4) the high electrophilicity index of TADs, and 5) the high asynchronycity found in the reaction performed with a steroidal model. Substituent and solvent effects are also analyzed

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Acknowledgments

The authors gratefully thank Conacyt (Grants 176863, 176858, and INFRA-2013-01-204586) and VIEP-BUAP (Grants VIEP-247-2013 and VIEP-098-2014). Moshinsky Foundation supported the work in Mérida. The CGSTIC (Xiuhcoalt) at Cinvestav is gratefully acknowledged for generous allocation of computational resources. LRD thanks Universidad de Valencia (Grant UV-INV-AE13-139082). CZ acknowledges Conacyt for the PhD fellowship.

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Correspondence to María A. Fernández-Herrera, Luis R. Domingo or Gabriel Merino.

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Fernández-Herrera, M.A., Zavala-Oseguera, C., Cabellos, J.L. et al. Understanding the high reactivity of triazolinediones in Diels-Alder reactions. A DFT study. J Mol Model 20, 2207 (2014). https://doi.org/10.1007/s00894-014-2207-7

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  • DOI: https://doi.org/10.1007/s00894-014-2207-7

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