title: On the (4)J(HH) long-range coupling in 2-bromocyclohexanone: conformational insights.
abstract: 2-Bromocyclohexanone is a model compound in which a 4JH2, H6 coupling constant is observed, whereas the corresponding 4JH2,H4 is absent. The observed long-range coupling is not only a result of the known W-type coupling, in the axial conformation, but also because of the less usual diaxial spin-spin coupling in the equatorial conformer. The carbonyl group plays a determining role in describing the coupling pathway, as concluded by natural bond orbital (NBO) analysis; although the sigma C2-H2-->sigma*C1(O)-C6 and sigma C6-H6 -->sigma*C1(O)-C2 interactions in the axial conformer contribute for transmitting the spin information associated with the W-type coupling, the strong sigma C2-H2-->pi*C=O and sigma C6-H6-->pi*C=O hyperconjugations in the equatorial conformer define an enhanced coupling pathway for 4JH2,H6,despite the inhibition of this coupling because of nO-->sigma*C(O)-C interaction and the large carbonyl angle. These findings provide the experimental evidence that orbital interactions contribute for the conformational isomerism of 2-bromocyclohexanone.
authors.affiliation: Departamento de Química, Universidade Federal de Lavras, CP 3037, 37200-000 Lavras, MG, Brazil.
authors.forename: Jakelyne V
authors.initials: JV
authors.lastname: Coelho
authors.forename: Matheus P
authors.initials: MP
authors.lastname: Freitas
authors.forename: Cláudio F
authors.initials: CF
authors.lastname: Tormena
authors.forename: Roberto
authors.initials: R
authors.lastname: Rittner
mesh_terms: D003512:Cyclohexanones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D012015:Reference Standards; D013237:Stereoisomerism
chemical_list: C540508:2-bromocyclohexanone; D003512:Cyclohexanones