The most reactive amide as a transition-state mimic for cis-trans interconversion.
Komarov, Igor V
Ishchenko, Aleksandr Yu
Davies, John E
Goodman, Jonathan M
Kirby, Anthony J
J Am Chem Soc
American Chemical Society (ACS)
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Komarov, I. V., Yanik, S., Ishchenko, A. Y., Davies, J. E., Goodman, J. M., & Kirby, A. J. (2015). The most reactive amide as a transition-state mimic for cis-trans interconversion.. J Am Chem Soc, 2 926-930. https://doi.org/10.1021/ja511460a
1-Azatricyclo[126.96.36.199(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".
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.
External DOI: https://doi.org/10.1021/ja511460a
This record's URL: https://www.repository.cam.ac.uk/handle/1810/246951
Attribution 2.0 UK: England & Wales
Licence URL: http://creativecommons.org/licenses/by/2.0/uk/
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