Investigation of the Effect of Turn Residues on Tetrapeptide Aldol Catalysts with β-Turn Propensity.

Autor:	Liu AY; Department of Chemistry, Macalester College, Saint Paul, Minnesota 55105, United States., Calicdan XA; Department of Chemistry, Macalester College, Saint Paul, Minnesota 55105, United States., Glover GN; Department of Chemistry, Macalester College, Saint Paul, Minnesota 55105, United States., Luo X; Department of Chemistry, Macalester College, Saint Paul, Minnesota 55105, United States., Barroso GT; Department of Chemistry, Macalester College, Saint Paul, Minnesota 55105, United States., Hoppe BK; Department of Chemistry, Macalester College, Saint Paul, Minnesota 55105, United States., Boyle KM; Department of Chemistry, Macalester College, Saint Paul, Minnesota 55105, United States., Witus LS; Department of Chemistry, Macalester College, Saint Paul, Minnesota 55105, United States.
Jazyk:	angličtina
Zdroj:	ACS omega [ACS Omega] 2022 Dec 01; Vol. 7 (49), pp. 45336-45340. Date of Electronic Publication: 2022 Dec 01 (Print Publication: 2022).
DOI:	10.1021/acsomega.2c05921
Abstrakt:	Peptide catalysts for a wide diversity of reaction types contain a common motif-residues that bias the sequence toward β-turn secondary structure. In this work, we explore what role that secondary structure plays in the catalysis of aldol reactions for primary amine tetrapeptide aldol catalysts. Using a lead tetrapeptide β-turn catalytic sequence, we varied the i + 1 and i + 2 residues to amino acids that would affect the β-turn propensity. We then studied the correlation between secondary structure, aldol rate enhancement, and stereoselectivity of the reaction between hydroxyacetone and 4-nitrobenzaldehyde. Using the i + 3 amide chemical shift as a measure of β-turn character, we found a rough correlation between the peptide structure and reaction kinetics but minimal effect on stereoselectivity. These trends may help aid the design of future catalytic sequences. Competing Interests: The authors declare no competing financial interest. (© 2022 The Authors. Published by American Chemical Society.)
Databáze:	MEDLINE
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