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Role of intramolecular hydrogen bonds and electron withdrawing groups in the acidity of aldimines and ketimines: a density functional theory study

  • Fernando Aguilar-Galindo
  • Ana María Tuñón
  • Alberto Fraile
  • José Alemán
  • Sergio Díaz-TenderoEmail author
Regular Article
  • 37 Downloads
Part of the following topical collections:
  1. 11th Congress on Electronic Structure: Principles and Applications (ESPA-2018)

Abstract

The role of intramolecular hydrogen bonds and the presence of electron withdrawing groups in the acidity of secondary aldimines and secondary ketimines is investigated by means of density functional theory simulations. We have found that the presence of an intramolecular hydrogen bond can increase the acidity up to ~ 20 kJ mol−1 with respect to structural isomers not showing it. In general, the excess of negative charge in the deprotonated species is hosted by the electron withdrawing group, thus stabilizing the anion and increasing the acidity. Among the studied structures, secondary ketimines, bearing a phenyl group, have shown to present the highest acidity and are therefore potential candidates that would be used for different Michael and nucleophilic additions in the synthesis of important pharmaceutical and natural products.

Keywords

Intramolecular hydrogen bond Electron withdrawing group Acidity Aldimine Ketimine Density functional theory 

Notes

Acknowledgements

The authors acknowledge the generous allocation of computer time at the Centro de Computación Científica of the Universidad Autonónoma de Madrid (CCC-UAM). This work was partially supported by the projects CTQ2016-76061-P & CTQ2015-64561-R of the Spanish Ministerio de Economía y Competitividad (MINECO). F.A.G. acknowledges the FPI grant associated with the project CTQ2013-43698-P (MINECO). Financial support from the MINECO through the “María de Maeztu” Program for Units of Excellence in R&D (MDM-2014-0377) is also acknowledged.

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Departamento de QuímicaUniversidad Autónoma de MadridMadridSpain
  2. 2.Departamento de Química, OrgánicaUniversidad Autónoma de MadridMadridSpain
  3. 3.Institute for Advanced Research in Chemical Sciences (IAdChem)Universidad Autónoma de MadridMadridSpain
  4. 4.Condensed Matter Physics Center (IFIMAC)Universidad Autónoma de MadridMadridSpain

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