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Electrophilic activation of CO2 in cycloaddition reactions towards a nucleophilic carbenoid intermediate: new defying insights from the Molecular Electron Density Theory

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Abstract

The electrophilic activation of the two C=O double bonds of CO2 in the cycloaddition reactions involved in the domino reaction between methyl isocyanide, acetylenedicarboxylate and CO2 yielding a spiro-compound has been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d,p) computational level. The approaching mode of the carbonyl groups of CO2 and lactone to the high nucleophilic carbenoid intermediate generated in the first reaction of this domino process promotes the C–C bond formation and the subsequent ring closure. MEDT analysis of cycloaddition reactions involved in this domino process enables to understand the molecular mechanism of these [2n + 2n] cycloadditions, which is different from the previously proposed [4π + 2π] cycloadditions derived from the Frontier Molecular Orbital theory.

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Acknowledgements

This work has been supported by the Ministerio de Economía y Competitividad of the Spanish Government, project CTQ2013-45646-P, Fondecyt (Chile) grants 1140341 and 1140343, Millennium Nucleus Chemical Processes and Catalysis (CPC) Project No. 120082 and the Universidad Andrés Bello (UNAB) for continuous support through research grants DI-806-15/R and DI-793-15/R. Prof L.R.D. also thanks FONDECYT for continuous support through Cooperación Internacional. M. R.-G. thanks the Ministerio de Economía y Competitividad for a predoctoral contract co-financed by the European Social Fund (BES-2014-068258).

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  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, Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Av. Republica 498, 8370146, Santiago, Chile

    Eduardo Chamorro & Patricia Pérez

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Domingo, L.R., Ríos-Gutiérrez, M., Chamorro, E. et al. Electrophilic activation of CO2 in cycloaddition reactions towards a nucleophilic carbenoid intermediate: new defying insights from the Molecular Electron Density Theory. Theor Chem Acc 136, 1 (2017). https://doi.org/10.1007/s00214-016-2022-6

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