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Stereoselective (exo-specific) synthesis, dynamic 1H NMR and quantum chemical conformational and configurational analysis of norbornene-aziridine-E-imidoyl system

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Abstract

Stereoselective (exo-specific) synthesis, dynamic 1H NMR and computational analysis of exo-N′-{3-azatricyclo[3.2.1.0.2,4]oct-3-yl)mesithyloxy)methylene}-1-benzensulfunamide (3) were investigated. Aziridine nitrogen inversion gives rise to two sets of configurations where the N-substituent is Syn (S) or Anti (A) to C7 of the norbornyl ring. At lower temperature, the proton signals of aziridine exo-E-3 decoalesces to show two syn conformers and one anti conformer (exo-E-31S \( \leftrightharpoons \) exo-E-32S \( \leftrightharpoons \) exo-E-33A) with ratio of 60:20:20, respectively. Experimentally, the Gibbs free energy of activations [ΔG‡ (kcal/mol)  ± 0.08] were calculated 11.96, 12.45 for 3 isomerizations. The standard Gibbs free energy (ΔGo kcal/mol) 0.174, 0, 0.174, and 0.298 at 213 K and energy minimum 6.64, 4.77 and 1.78 were calculated for 31S \( \leftrightharpoons \) 32S, 32S \( \leftrightharpoons \) 33A, 31S \( \leftrightharpoons \) 33A isomerizations, respectively. The enthalpy (ΔH‡, kcal/mol) and entropy (ΔS‡, cal mol−1 K−1) of activation for the nitrogen inversion of aziridine of 3 were calculated 11.2 and −0.80, respectively.

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Acknowledgments

We would like to thank Isfahan University of Technology (IUT) for the financial support (Research Council Grant).

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Authors and Affiliations

  1. Department of Chemistry, Isfahan University of Technology, 8415483111, Isfahan, Iran

    Hossein A. Dabbagh & Alireza Najafi Chermahini

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  1. Hossein A. Dabbagh
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  2. Alireza Najafi Chermahini
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Correspondence to Hossein A. Dabbagh.

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Dabbagh, H.A., Najafi Chermahini, A. Stereoselective (exo-specific) synthesis, dynamic 1H NMR and quantum chemical conformational and configurational analysis of norbornene-aziridine-E-imidoyl system. J IRAN CHEM SOC 9, 339–348 (2012). https://doi.org/10.1007/s13738-011-0029-4

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