Detection and Verification of a Key Intermediate in an Enantioselective Peptide Catalyzed Acylation Reaction
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 interme...
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| Format: | Article |
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MDPI AG
2022-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/19/6351 |
| _version_ | 1797477990180847616 |
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| author | Matthias Brauser Tim Heymann Christina Marie Thiele |
| author_facet | Matthias Brauser Tim Heymann Christina Marie Thiele |
| author_sort | Matthias Brauser |
| collection | DOAJ |
| description | 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 <i>trans</i>-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 <i>trans</i>-cyclohexane-1,2-diol. These findings are important steps towards the understanding of this highly enantioselective organocatalyst. |
| first_indexed | 2024-03-09T21:25:38Z |
| format | Article |
| id | doaj.art-619c6c3c0074483b8c114c83654a2022 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T21:25:38Z |
| publishDate | 2022-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-619c6c3c0074483b8c114c83654a20222023-11-23T21:09:53ZengMDPI AGMolecules1420-30492022-09-012719635110.3390/molecules27196351Detection and Verification of a Key Intermediate in an Enantioselective Peptide Catalyzed Acylation ReactionMatthias Brauser0Tim Heymann1Christina Marie Thiele2Clemens-Schöpf-Institute for Organic Chemistry and Biochemistry, Department of Chemistry, Technical University of Darmstadt, Alarich-Weiss-Straße 4, 64287 Darmstadt, GermanyClemens-Schöpf-Institute for Organic Chemistry and Biochemistry, Department of Chemistry, Technical University of Darmstadt, Alarich-Weiss-Straße 4, 64287 Darmstadt, GermanyClemens-Schöpf-Institute for Organic Chemistry and Biochemistry, Department of Chemistry, Technical University of Darmstadt, Alarich-Weiss-Straße 4, 64287 Darmstadt, GermanyUntil 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 <i>trans</i>-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 <i>trans</i>-cyclohexane-1,2-diol. These findings are important steps towards the understanding of this highly enantioselective organocatalyst.https://www.mdpi.com/1420-3049/27/19/6351acylationimidazolium ionmass spectrometryNMR spectroscopyorganocatalysis |
| spellingShingle | Matthias Brauser Tim Heymann Christina Marie Thiele Detection and Verification of a Key Intermediate in an Enantioselective Peptide Catalyzed Acylation Reaction Molecules acylation imidazolium ion mass spectrometry NMR spectroscopy organocatalysis |
| title | Detection and Verification of a Key Intermediate in an Enantioselective Peptide Catalyzed Acylation Reaction |
| title_full | Detection and Verification of a Key Intermediate in an Enantioselective Peptide Catalyzed Acylation Reaction |
| title_fullStr | Detection and Verification of a Key Intermediate in an Enantioselective Peptide Catalyzed Acylation Reaction |
| title_full_unstemmed | Detection and Verification of a Key Intermediate in an Enantioselective Peptide Catalyzed Acylation Reaction |
| title_short | Detection and Verification of a Key Intermediate in an Enantioselective Peptide Catalyzed Acylation Reaction |
| title_sort | detection and verification of a key intermediate in an enantioselective peptide catalyzed acylation reaction |
| topic | acylation imidazolium ion mass spectrometry NMR spectroscopy organocatalysis |
| url | https://www.mdpi.com/1420-3049/27/19/6351 |
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