The most reactive amide as a transition-state mimic for cis-trans interconversion.
Type
Article
Change log
Authors
Komarov, Igor V
Yanik, Stanislav
Ishchenko, Aleksandr Yu
Davies, John E
Goodman, Jonathan M
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".
Description
Keywords
Amides, Aza Compounds, Heterocyclic Compounds, 3-Ring, Models, Molecular, Molecular Conformation, Stereoisomerism
Journal Title
J Am Chem Soc
Conference Name
Journal ISSN
0002-7863
1520-5126
1520-5126
Volume Title
2
Publisher
American Chemical Society (ACS)
Publisher DOI
Sponsorship
Financial assistance from Enamine Ltd. (www.enamine.net) is
gratefully acknowledged. We also thank Dr. V. Stepanenko for
valuable advice and encouragement which helped to find the
nonstandard solutions to the synthetic problems, and Vitaliy
Bilenko for drawing our attention to the instructive EI mass
spectrum of compound 8.