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Cis/Trans Energetics in Epoxide, Thiirane, Aziridine and Phosphirane Containing Cyclopentanols: Effects of Intramolecular OH⋯O, S, N and P Contacts

1
Department of Chemistry and Biochemistry, University of Mississippi, 322 Coulter Hall, University, MS 38677-1848, USA
2
Chemistry Department, Central Alabama Community College, 1675 Cherokee Road, Alexander City, AL 35010, USA
*
Author to whom correspondence should be addressed.
Academic Editors: Goar Sánchez, Steve Scheiner and John M. Herbert
Molecules 2019, 24(14), 2523; https://doi.org/10.3390/molecules24142523
Received: 14 March 2019 / Revised: 24 June 2019 / Accepted: 3 July 2019 / Published: 10 July 2019
(This article belongs to the Special Issue Intramolecular Hydrogen Bonding 2018)
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Abstract

A recent computational analysis of the stabilizing intramolecular OH⋯O contact in 1,2-dialkyl-2,3-epoxycyclopentanol diastereomers has been extended to thiiriane, aziridine and phosphirane analogues. Density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2) and CCSD(T) coupled-cluster computations with simple methyl and ethyl substituents indicate that electronic energies of the c i s isomers are lowered by roughly 3 to 4 kcal mol−1 when the OH group of these cyclopentanol systems forms an intramolecular contact with the O, S, N or P atom on the adjacent carbon. The results also suggest that S and P can participate in these stabilizing intramolecular interactions as effectively as O and N in constrained molecular environments. The stabilizing intramolecular OH⋯O, OH⋯S, OH⋯N and OH⋯P contacts also increase the covalent OH bond length and significantly decrease the OH stretching vibrational frequency in every system with shifts typically on the order of −41 cm−1. View Full-Text
Keywords: intramolecular hydrogen bonding; semipinacol rearrangement; vibrational frequencies; density functional theory (DFT); coupled-cluster theory intramolecular hydrogen bonding; semipinacol rearrangement; vibrational frequencies; density functional theory (DFT); coupled-cluster theory
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Smith, B.E.; Carr, J.M.; Tschumper, G.S. Cis/Trans Energetics in Epoxide, Thiirane, Aziridine and Phosphirane Containing Cyclopentanols: Effects of Intramolecular OH⋯O, S, N and P Contacts. Molecules 2019, 24, 2523.

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