title: The most reactive amide as a transition-state mimic for cis-trans interconversion.
abstract: 1-Azatricyclo[3.3.1.1(3,7)]decan-2-one (3), the parent compound of a rare class of 90°-twisted amides, has finally been synthesized, using an unprecedented transformation. These compounds are of special interest as transition-state mimics for the enzyme-catalyzed cis-trans rotamer interconversion of amides involved in peptide and protein folding and function. The stabilization of the amide group in its high energy, perpendicular conformation common to both systems is shown for the rigid tricyclic system to depend, as predicted by calculation, on its methyl group substitution pattern, making 3 by some way the most reactive known "amide".
authors.affiliation: Institute of High Technologies and ‡Chemistry Department, Taras Shevchenko National University of Kyiv , Volodymyrska 60 and 64, 01601 Kyiv, Ukraine.
authors.forename: Igor V
authors.initials: IV
authors.lastname: Komarov
authors.forename: Stanislav
authors.initials: S
authors.lastname: Yanik
authors.forename: Aleksandr Yu
authors.initials: AY
authors.lastname: Ishchenko
authors.forename: John E
authors.initials: JE
authors.lastname: Davies
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: Goodman
authors.forename: Anthony J
authors.initials: AJ
authors.lastname: Kirby
mesh_terms: D000577:Amides / Q000737:chemistry*; D001372:Aza Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D006575:Heterocyclic Compounds, 3-Ring / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: C000601775:1-azatricyclo(3.3.1.1(3,7))decan-2-one; D000577:Amides; D001372:Aza Compounds; D006575:Heterocyclic Compounds, 3-Ring