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Abstract:

The conformational equilibria of cyclohexane (as well as its fluoro-, chloro-, methyl-, hydroxy-, and t-butyl derivatives), cyclohexanone, piperidine, tetrahydropyran (and its 2-hydroxy derivative) were studied by ab initio and DFT procedures. The transition states were calculated at HF/6-31G, B3LYP/6-31+G*, and B3LYP/6-311+G* levels, whereas the intrinsic reaction coordinates (IRCs) were evaluated at the B3LYP/6-31+G* level. The degree of puckering and energy data was nearly not basis set-dependent (using B3LYP) in most of the cases. However, DFT methods gave better agreement with experimental data than HF methods, as expected from electron correlation inclusion. Fluorocyclohexane and 2-hydroxytetrahydropyran showed the largest basis set-energy dependence. It was found that the conversion from chair to skew is direct in some cases, whereas in others it goes through the pseudorotational (skew/boat) pathway. The case of t-butylcyclohexane, with a skew form as stable as one of the chairs, is especially interesting. In this compound, as well as in cyclohexanone and 2-hydroxytetrahydropyran, large deviations from the known pseudorotation/inversion scheme are observed. Copyright © 2010 John Wiley & Sons, Ltd.

Registro:

Documento: Artículo
Título:Conformational pathways of simple six-membered rings
Autor:Stortz, C.A.
Filiación:Departamento de Química Orgánica-CIHIDECAR, Facultad de Ciencias Exactas y Naturales, UBA, Ciudad Universitaria, Pab. 2, 1428 Buenos Aires, Argentina
Palabras clave:conformational analysis; cyclohexane; density functional calculations; six-membered rings; transition states; Ab initio and DFT; Basis sets; Conformational analysis; Conformational equilibrium; Conformational pathways; Cyclohexanones; Density-functional calculations; DFT method; Energy data; Energy dependence; Experimental data; HF/6-31G; Hydroxyderivative; Hydroxytetrahydropyran; Intrinsic reaction coordinate; Large deviations; Six-membered rings; Tetrahydropyran; Transition state; Cyclohexane; Density functional theory; Conformations
Año:2010
Volumen:23
Número:12
Página de inicio:1173
Página de fin:1186
DOI: http://dx.doi.org/10.1002/poc.1689
Título revista:Journal of Physical Organic Chemistry
Título revista abreviado:J Phys Org Chem
ISSN:08943230
CODEN:JPOCE
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v23_n12_p1173_Stortz

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Citas:

---------- APA ----------
(2010) . Conformational pathways of simple six-membered rings. Journal of Physical Organic Chemistry, 23(12), 1173-1186.
http://dx.doi.org/10.1002/poc.1689
---------- CHICAGO ----------
Stortz, C.A. "Conformational pathways of simple six-membered rings" . Journal of Physical Organic Chemistry 23, no. 12 (2010) : 1173-1186.
http://dx.doi.org/10.1002/poc.1689
---------- MLA ----------
Stortz, C.A. "Conformational pathways of simple six-membered rings" . Journal of Physical Organic Chemistry, vol. 23, no. 12, 2010, pp. 1173-1186.
http://dx.doi.org/10.1002/poc.1689
---------- VANCOUVER ----------
Stortz, C.A. Conformational pathways of simple six-membered rings. J Phys Org Chem. 2010;23(12):1173-1186.
http://dx.doi.org/10.1002/poc.1689