Manifestation of Stereoelectronic Effects on the Calculated Carbon−Hydrogen Bond Lengths and One Bond1JC-HNMR Coupling Constants in Cyclohexane, Six-Membered Heterocycles, and Cyclohexanone Derivatives
- 15 October 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (44) , 13088-13096
- https://doi.org/10.1021/ja020317u
Abstract
Cyclohexane (1), oxygen-, sulfur-, and/or nitrogen-containing six-membered heterocycles 2−5, cyclohexanone (6), and cyclohexanone derivatives 7−16 were studied theoretically [B3LYP/6-31G(d,p) and PP/IGLO−III//B3LYP/6-31G(d,p) methods] to determine the structural (in particular C−H bond distances) and spectroscopic (specifically, one bond 1JC-H NMR coupling constants) consequences of stereoelectronic hyperconjugative effects. The results confirm the importance of nX → σ*C-Ηapp (where X = O, N), σC-Hax → π*CO, σS-C → σ*C-Ηapp, σC-S→σ*C-Ηapp, β-nO → σ*C-H, and σC-H → σ*C-Ηapp hyperconjugation, as advanced in previous theoretical models. Calculated rC-H bond lengths and 1JC-H coupling constants for C−H bonds participating in more than one hyperconjugative interaction show additivity of the effects.Keywords
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