Conformation analyses, dynamic behavior and amide bond distortions of medium-sized heterocycles. 1. Partially and fully reduced 1-benzazepines.
Five 1-benzazepine heterocycles were synthesized by utilizing transition-metal-catalyzed processes in key bond-forming steps. exo-Methylene and methyl substituents were introduced at position 5, as well as a unit of unsaturation between positions 3 and 4, with benzoyl or benzyl N-substituents. Solution- and solid-state structures were examined, using dynamic NMR spectroscopy and X-ray crystallography, corroborated by molecular mechanics calculations. Greater amide distortion is associated with a more stable ground-state structure, which is in turn more reluctant to undergo conformational changes.
Qadir
Maryiam
M
Department of Chemistry, King's College London, Strand WC2R 2LS, UK.
Cobb
Jonathan
J
Sheldrake
Peter W
PW
Whittall
Neil
N
White
Andrew J P
AJ
Hii
King Kuok Mimi
KK
Horton
Peter N
PN
Hursthouse
Michael B
MB
D000577:Amides / Q000737:chemistry*; D001552:Benzazepines / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003500:Cyclization; D006574:Heterocyclic Compounds, 2-Ring / Q000138:chemical synthesis / Q000737:chemistry*; D008956:Models, Chemical; D008968:Molecular Conformation; D013329:Structure-Activity Relationship
D000577:Amides; D001552:Benzazepines; D006574:Heterocyclic Compounds, 2-Ring