Insight into the intramolecular interactions of trans-2-azidocycloalk-3-en-1-ols and trans-2-azidocycloalk-3-en-1-yl acetates: A theoretical study

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Çetinkaya Y., Maraş A., Göksu S.

TETRAHEDRON, cilt.92, 2021 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 92
  • Basım Tarihi: 2021
  • Doi Numarası: 10.1016/j.tet.2021.132272
  • Dergi Adı: TETRAHEDRON
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Aquatic Science & Fisheries Abstracts (ASFA), BIOSIS, Biotechnology Research Abstracts, CAB Abstracts, Chemical Abstracts Core, Chimica, EMBASE, Veterinary Science Database
  • Anahtar Kelimeler: Allylic azide, Winstein rearrangement, Intramolecular interactions, Density functional theory, NBO, BIASED 3,3-SIGMATROPIC REARRANGEMENT, ALLYLIC AZIDE, DENSITY FUNCTIONALS, EFFICIENT, THERMOCHEMISTRY, DERIVATIVES, HARDNESS
  • Atatürk Üniversitesi Adresli: Evet

Özet

In this study, dedicated to Prof. Dr. Yasar Sutbeyaz (1950e2016), intramolecular interactions in (1S(R),2S(R))-2-azidocycloalk-3-en-1-ols and (1S(R),2S(R))-2-azidocycloalk-3-en-1-yl acetates consisting of six-to eight-membered rings were investigated by molecular spectroscopy and density functional theory calculations including three different functional levels, B3LYP, M06-2X and omega B97XD with the 6-31 +G(d,p) basis set. These allylic azides stabilized by intramolecular OH center dot center dot center dot N and CH center dot center dot center dot N interactions did not cause the Winstein rearrangement known as the 1,3-allylic azide rearrangement or [3,3]-sigmatropic rearrangement. The results of the structural parameters, relative total energies, natural bond orbital analysis of donor-acceptor interactions and charges on the atoms support why the Winstein rearrangement does not occur. The quantum chemical reactivity identifiers and molecular electrostatic potential were analyzed using the M062X/6-31+G(d,p) basis set. (c) 2021 Elsevier Ltd. All rights reserved.