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Understanding the reaction mechanism of the Lewis acid (MgBr2)-catalysed [3+2] cycloaddition reaction between C-methoxycarbonyl nitrone and 2-propen-1-ol: a DFT study

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Abstract

The mechanism of the non-catalysed and the MgBr2-catalysed [3+2] cycloaddition (32CA) reactions between C-methoxycarbonyl nitrone and 2-propen-1-ol has been theoretically investigated within the molecular electron density theory using DFT methods at the B3LYP/6-31G(d) computational level. Analysis of DFT reactivity indices allows explaining the role of the MgBr2 Lewis acid in the catalysed 32CA reaction. The 32CA reaction between C-methoxycarbonyl nitrone and 2-propen-1-ol takes place with a relative high activation enthalpy, 13.5 kcal mol−1, as a consequence of the non-polar character of this zw-type 32CA reaction. Coordination of the MgBr2 LA to C-methoxycarbonyl nitrone accelerates the corresponding zw-type 32CA reaction by taking place through a polar mechanism and with lower activation enthalpy, 8.5 kcal mol−1. Both 32CA reactions, which take place through a one-step mechanism, are completely meta regioselective and present low exo stereoselectivity, which increases in the catalysed process. Energy and non-covalent interaction analyses at the transition-state structures indicate that the formation of an intramolecular H–Br hydrogen bond in the catalysed process could be responsible for the exo selectivity experimentally observed.

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Acknowledgements

This work has been supported by the Ministry of Economy and Competitiveness of the Spanish Government; Project CTQ2013-45646-P. M. Ríos-Gutiérrez also thanks the Ministry of Economy and Competitiveness for a pre-doctoral contract co-financed by the European Social Fund (BES-2014-068258). A.I. Adjieufack, I. M. Ndassa and J. K. Mbadcam are grateful to the Ministry of Higher Education of the Republic of Cameroon to finance the project with modernisation research allowance. The authors also thank the University of Yaoundé I and High Teacher Training College (Cameroon) for infrastructural facilities for generous allocation of computer time.

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Authors and Affiliations

  1. Physical and Theoretical Chemistry Laboratory, Faculty of Science, University of Yaoundé I, P.O. Box 812, Yaoundé, Cameroon

    A. I. Adjieufack & J. Ketcha Mbadcam

  2. Department of Chemistry, High Teacher Training College, University of Yaoundé I, P. O. Box 47, Yaoundé, Cameroon

    I. M. Ndassa

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

    M. Ríos-Gutiérrez & L. R. Domingo

Authors
  1. A. I. Adjieufack
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  2. I. M. Ndassa
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  3. J. Ketcha Mbadcam
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  4. M. Ríos-Gutiérrez
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  5. L. R. Domingo
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Correspondence to I. M. Ndassa or L. R. Domingo.

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Adjieufack, A.I., Ndassa, I.M., Mbadcam, J.K. et al. Understanding the reaction mechanism of the Lewis acid (MgBr2)-catalysed [3+2] cycloaddition reaction between C-methoxycarbonyl nitrone and 2-propen-1-ol: a DFT study. Theor Chem Acc 136, 5 (2017). https://doi.org/10.1007/s00214-016-2028-0

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