Ring inversion barriers
Analytical Chemistry and Spectroscopy
Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
The dynamic 1H and 13C NMR spectra of a series of mono- and bis-annelated 4,9-dihetero-(Z,Z)-cyclodeca-1,6-dienes were obtained and are discussed with respect to ground-state conformers and the barriers to ring inversion, and to the restricted rotation about exocyclic partial C,N double bonds. The ten-membered rings are, with one exception, anancomeric chair conformers and interconvert via a combination of single bond rotations and bond angle bendings. Depending on the heteroatoms present, the series of decreasing barriers to ring inversion S 〉 NH 〉 O was obtained. Benzannelation decreases the free energy of activation of the same dynamic process owing to greater intramolecular transannular H,H interactions.
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