Research on Chemical Intermediates

, Volume 43, Issue 2, pp 767–782 | Cite as

Regioselectivity of 1,3-dipolar cycloadditions between aryl azides and an electron-deficient alkyne through DFT reactivity descriptors

  • Nazli Javani Dizaji
  • Azita Nouri
  • Ehsan Zahedi
  • Seyed Majid Musavi
  • Arezu Nouri


Conceptual density functional theory, including chemical hardness, electronic chemical potential, global and local electrophilicity index and Fukui functions, is used to predict reactivity and regioselectivity of 1,3-dipolar cycloadditions (13DCs) between five aryl azides (1–5) and an electron-deficient alkyne at the B3LYP/6-31G(d,p) level. Two reaction paths (a) and (b) are considered which result in the corresponding regioisomeric 1,2,3-triazoles P(1-5)a and P(1-5)b, respectively. All the 13DCs proceed via rather asynchronous TSs and the path (b) is clearly more synchronous than the path (a). All the reactions are high exoergic [∆Gº = −45.1 to −51.4 kcal/mol for path (a) and −47.7 to −55.9 kcal/mol for path (b)] with the moderate and nearly similar activation barriers (E a  = 15.4–16.7 kcal/mol) referring a relatively low regioselectivity. All reactivity descriptors but one clearly suggest that path (a) is somewhat preferred over path (b). FMO interactions occur between HOMO13DP and LUMODPh due to the corresponding lower energy gap. All the reactions considered in this work classified as polar 13DCs with NED character. Our theoretical results are in good agreement with those reported experimentally.


1,3-Dipolar cycloadditions Conceptual DFT Fukui function Gazquez–Mendez rule HSAB 



The authors gratefully acknowledge The Research Council of the Islamic Azad University Shahr-e-Qods Branch.


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Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  • Nazli Javani Dizaji
    • 1
  • Azita Nouri
    • 1
  • Ehsan Zahedi
    • 2
  • Seyed Majid Musavi
    • 1
  • Arezu Nouri
    • 3
  1. 1.Department of Chemistry, Shahr-e Qods BranchIslamic Azad UniversityTehranIran
  2. 2.Department of Chemistry, Shahrood BranchIslamic Azad UniversityShahroodIran
  3. 3.Central LaboratoryIran Polymer and Petrochemical InstituteTehranIran

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