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Organocatalytic access to a cis-Cyclopentyl-gamma-amino acid: an intriguing model of selectivity and formation of a stable 10/12-helix from the corresponding gamma/alpha-peptide

Fanelli, R., Berta, D., Foldes, T., Rosta, E., Atkinson, R. A., Hofmann, H.-J., Shankland, K. and Cobb, A. (2020) Organocatalytic access to a cis-Cyclopentyl-gamma-amino acid: an intriguing model of selectivity and formation of a stable 10/12-helix from the corresponding gamma/alpha-peptide. Journal of the American Chemical Society, 142 (3). pp. 1382-1393. ISSN 1520-5126

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To link to this item DOI: 10.1021/jacs.9b10861

Abstract/Summary

In this study, we have developed a highly enantioselective organocatalytic route to the (1S,2R)-2-(aminomethyl)cyclopentane-1-carboxylic acid monomer precursor, which has a cis-configuration between the C- and N-termini around the cyclopentane core. Kinetic measurements show that the product distribution changes over time due to epimerization of the C1 center. Computations suggest the cis-selectivity is a result of selective C-C bond formation, whilst subsequent steps appear to infuence the selectivity at higher temperature. The resulting gamma-amino acid residue was incorporated into a novel gamma/alpha-peptide which forms a well-ordered 10/12-helix with alternate H-bond directionality in spite of the smallest value of the zeta-angle yet observed for a helix of this type. This highly dened structure is a result of the narrow range of potential zeta-angles in our monomer. In contrast, the larger range of potential zeta-values observed for the corresponding trans-system can be fulfilled by several competing helical structures.

Item Type:Article
Refereed:Yes
Divisions:Interdisciplinary centres and themes > Chemical Analysis Facility (CAF)
Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > School of Pharmacy > Pharmaceutics Research Group
ID Code:88074
Publisher:American Chemical Society

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