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Título: | Density Functional Theory Computational Reexamination of the Anomeric Effect in 2-Methoxy- and 2-Cyano-1,3-dioxanes and 1,3-Dithianes. Stereoelectronic Interactions Involving the Cyano (C=N:) Group Revealed by Natural Bond Orbital (NBO) Analysis |
Autor: | Juaristi, E.; Notario, Rafael CSIC ORCID | Fecha de publicación: | 2018 | Editor: | American Chemical Society | Citación: | Journal of Organic Chemistry 83: 10326- 10333 (2018) | Resumen: | This study reports DFT geometry optimization of the anancomeric (ring conformationally anchored) axial r2-methoxy-trans-4,trans-6-dimethyl- and r-2-cyano-trans-4,trans-6-dimethyl-1,3-dioxanes (1-ax and 3-ax, respectively), the equatorial isomers (2-eq and 4-eq, respectively), the axial r2-methoxy- and r2-cyano-trans-4,trans-6-dimethyl-1,3-dithianes (5-ax and 7-ax, respectively), and the equatorial isomers (6-eq and 8-eq, respectively). The computational results reproduce the anomeric effect in 1-8, and most importantly, Weinhold's NBO analysis supports the contribution of n(X) → σ∗(C-Y) stereoelectronic interactions that stabilize the axial isomers. Furthermore, NBO analysis of delocalization energy E(2) of properly aligned filled/empty orbitals in these isomeric 2-polar-substituted heterocycles reveals that n(O) → σ∗(C-H) is responsible for the increased charge density at C(2)-H in the equatorial isomers, providing an explanation for the computational observation that very recently led Wiberg, Bailey, Lambert, and Stempel (J. Org. Chem. 2018, 83, 5242-5255) to discard a potential contribution of n(X) → σ∗(C-Y) stereoelectronic interactions that stabilize the axial isomers. Interestingly, during the course of this study, two relevant stereoelectronic interactions involving the cyano group were revealed, n(N) → σ∗(NC-C) and σ(C(2)-H) → σ∗(C-N). | URI: | http://hdl.handle.net/10261/179360 | DOI: | 10.1021/acs.joc.8b01458 | Identificadores: | doi: 10.1021/acs.joc.8b01458 issn: 1520-6904 |
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