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Tertiary aromatic amides bearing stereogenic centres ortho to the amide group may adopt two diastereoisomeric conformations which interconvert slowly on the NMR timescale at ambient temperature, and are therefore detectable by NMR. Certain classes of stereogenic centre--particularly sulfoxides, ephedrine-derived oxazolidines, and proline-derived imidazolidines--strongly bias the population of the two conformers. We propose a model, supported by molecular mechanics calculations, which rationalises the sense and magnitude of the conformational selectivity attained in terms of the steric and electronic properties of the controlling centre. The control over conformation may be exploited either by trapping the favoured conformer as an atropisomer, or by using it to relay information about the stereochemistry of the controlling centre.

Original publication




Journal article


Org Biomol Chem

Publication Date





424 - 443


Alkylation, Amides, Crystallography, X-Ray, Ephedrine, Hydroxylation, Kinetics, Magnetic Resonance Spectroscopy, Models, Chemical, Molecular Conformation, Oxazoles, Proline, Stereoisomerism, Sulfur, Thermodynamics