期刊
MOLECULES
卷 27, 期 19, 页码 -出版社
MDPI
DOI: 10.3390/molecules27196351
关键词
acylation; imidazolium ion; mass spectrometry; NMR spectroscopy; organocatalysis
资金
- Deutsche Forschungsgesellschaft (DFG) [TH1115/12-1]
- Hans Messer Foundation
In this study, the intermediate responsible for the acyl transfer in a highly enantioselective tetrapeptide organocatalyst was successfully detected and characterized using NMR-spectroscopy and mass spectrometry. The formation of complexes between the tetrapeptide and trans-cyclohexane-1,2-diols was also observed, along with monitoring of the acetylation reaction. These findings provide important insights into the understanding of this organocatalyst's mechanism.
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 pi-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 trans-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 trans-cyclohexane-1,2-diol. These findings are important steps towards the understanding of this highly enantioselective organocatalyst.
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