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Understanding the carbenoid-type reactivity of nitrile ylides in [3+2] cycloaddition reactions towards electron-deficient ethylenes: a molecular electron density theory study

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Abstract

The [3+2] Cycloaddition (32CA) reaction of nitrile ylide (NY) 10 with electron-deficient ethylene 11 has been studied within the molecular electron density theory through DFT calculations at the MPWB1K/6-31G(d) computational level. A structural analysis of NY 10 indicates that this three-atom component has a carbenoid structure, allowing its participation in carbenoid-type (cb-type) 32CA reactions. This 32CA reaction takes place through a one-step mechanism with very low activation energy, 2.3 kcal mol−1. In gas phase, this 32CA reaction is not stereoselective and has low regioselectivity. Inclusion of solvent effects does not modify the activation energy, but increases the meta regioselectivity in clear agreement with the experimental outcomes. Electron localisation function topological analysis for the formation of the two C–C single bonds along the four competitive channels associated with this 32CA reaction makes it possible to characterise two dissimilar mechanisms. Along the more favourable meta regioisomeric channels, the 32CA reaction takes place through a two-stage one-step mechanism, while along the ortho regioisomeric channels it takes place via a synchronous C–C bond formation process.

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Acknowledgments

This work is in honour of the 60th birthday of Professor Alberto Vela. This work has been supported by the Ministry of Economy and Competitiveness of the Spanish Government, project CTQ2013-45646-P, Fondecyt (Chile) grants 1140341 (P.P.), 1140343 (E.C.) and 11130589 (M.D.-N), Millennium Nucleus Chemical Processes and Catalysis (CPC) project No. 120082 and the Universidad Andrés Bello (UNAB) for continuous support through research grants DI-793-15/R and DI-806-15/R. Prof L.R.D. also thanks FONDECYT for continuous support through Cooperación Internacional. M. R.-G. thanks the Ministry of Economy and Competitiveness for a pre-doctoral contract co-financed by the European Social Fund (BES-2014-068258).

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Authors and Affiliations

  1. Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain

    Luis R. Domingo & Mar Ríos-Gutiérrez

  2. Millennium Nucleus Chemical Processes and Catalysis (CPC), Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Av. República 230, 8370146, Santiago, Chile

    Mario Duque-Noreña, Eduardo Chamorro & Patricia Pérez

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  1. Luis R. Domingo
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  2. Mar Ríos-Gutiérrez
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  3. Mario Duque-Noreña
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  4. Eduardo Chamorro
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  5. Patricia Pérez
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Correspondence to Luis R. Domingo or Patricia Pérez.

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Published as part of the special collection of articles “Festschrift in honour of A. Vela”.

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Domingo, L.R., Ríos-Gutiérrez, M., Duque-Noreña, M. et al. Understanding the carbenoid-type reactivity of nitrile ylides in [3+2] cycloaddition reactions towards electron-deficient ethylenes: a molecular electron density theory study. Theor Chem Acc 135, 160 (2016). https://doi.org/10.1007/s00214-016-1909-6

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