Detection and Verification of a Key Intermediate in an Enantioselective Peptide Catalyzed Acylation Reaction

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2022 Oct 14

PMID 36234884

Authors

Matthias Brauser

Tim Heymann

Christina Marie Thiele

Affiliations

Soon will be listed here.

Abstract

Until now, the intermediate responsible for the acyl transfer of a highly enantioselective tetrapeptide organocatalyst for the kinetic resolution of trans-cycloalkane-1,2-diols has never been directly observed. It was proposed computationally that a π-methylhistidine moiety is acylated as an intermediate step in the catalytic cycle. In this study we set out to investigate whether we can detect and characterize this key intermediate using NMR-spectroscopy and mass spectrometry. Different mass spectrometric experiments using a nano-ElectroSpray Ionization (ESI) source and tandem MS-techniques allowed the identification of tetrapeptide acylium ions using different acylation reagents. The complexes of -cyclohexane-1,2-diols with the tetrapeptide were also detected. Additionally, we were able to detect acylated tetrapeptides in solution using NMR-spectroscopy and monitor the acetylation reaction of a -cyclohexane-1,2-diol. These findings are important steps towards the understanding of this highly enantioselective organocatalyst.

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