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Histidine-based copper tetrapeptides as enantioselective catalysts for aldol reactions
Copper(ii)-peptides are widely used as industrial catalysts such as in the aerobic oxidation of organic molecules, formation of new C–H bonds and in the azide–alkyne cycloaddition reaction. The length of peptides and the effect of adding copper metal into peptides were questioned in their field of a...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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The Royal Society of Chemistry
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9086720/ https://www.ncbi.nlm.nih.gov/pubmed/35548802 http://dx.doi.org/10.1039/c8ra06814c |
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author | Sharifa Zaithun, Begum Emilia, AbdulMalek Mohamed Ibrahim Mohamed, Tahir Karen Anne, Crouse Mohd Basyaruddin, Abdul Rahman |
author_facet | Sharifa Zaithun, Begum Emilia, AbdulMalek Mohamed Ibrahim Mohamed, Tahir Karen Anne, Crouse Mohd Basyaruddin, Abdul Rahman |
author_sort | Sharifa Zaithun, Begum |
collection | PubMed |
description | Copper(ii)-peptides are widely used as industrial catalysts such as in the aerobic oxidation of organic molecules, formation of new C–H bonds and in the azide–alkyne cycloaddition reaction. The length of peptides and the effect of adding copper metal into peptides were questioned in their field of applications. Five novel histidine-based tetrapeptides with the sequences HAAD (P1), HAFD (P2), HAVD (P3), AGHD (P4) and PGHD (P5) were synthesized using the solid phase peptide scheme and analysed with high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS) with percentage purities as high as 99.5%. All the peptides were positively charged (+1) and the molecular weight calculated from m/z values of MS results coincided with the theoretical molecular weight of the peptides. Copper(ii)-peptides derived from these peptides and copper(ii) acetate monohydrate (CuP1–CuP5) in a 1 : 2 ratio was synthesised, purified and characterised by ultraviolet-visible spectroscopy (UV-Vis), ultraviolet-fluorescence spectroscopy (fluorescence) and fourier transform infrared spectroscopy (FTIR), circular dichroism spectroscopy (CD) and optical rotation polarimetry. It provided the necessary information on the secondary structure and the successful binding of copper(ii) to the specific amino acids, hence leading to the putative geometry of copper(ii)-peptides and the difference in the chirality of amino acids, peptides and copper(ii)-peptides. The catalytic activities of the synthesised complexes were evaluated. CuP1 & CuP3 catalysed both the asymmetric aldol reactions with high enantioselectivity of p-nitrobenzaldehyde with cyclohexanone (% ee = 87.3 & 80.3, respectively) and of p-anisaldehyde with cyclohexanone (% ee = 95.5 & 90.9, respectively). |
format | Online Article Text |
id | pubmed-9086720 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-90867202022-05-10 Histidine-based copper tetrapeptides as enantioselective catalysts for aldol reactions Sharifa Zaithun, Begum Emilia, AbdulMalek Mohamed Ibrahim Mohamed, Tahir Karen Anne, Crouse Mohd Basyaruddin, Abdul Rahman RSC Adv Chemistry Copper(ii)-peptides are widely used as industrial catalysts such as in the aerobic oxidation of organic molecules, formation of new C–H bonds and in the azide–alkyne cycloaddition reaction. The length of peptides and the effect of adding copper metal into peptides were questioned in their field of applications. Five novel histidine-based tetrapeptides with the sequences HAAD (P1), HAFD (P2), HAVD (P3), AGHD (P4) and PGHD (P5) were synthesized using the solid phase peptide scheme and analysed with high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS) with percentage purities as high as 99.5%. All the peptides were positively charged (+1) and the molecular weight calculated from m/z values of MS results coincided with the theoretical molecular weight of the peptides. Copper(ii)-peptides derived from these peptides and copper(ii) acetate monohydrate (CuP1–CuP5) in a 1 : 2 ratio was synthesised, purified and characterised by ultraviolet-visible spectroscopy (UV-Vis), ultraviolet-fluorescence spectroscopy (fluorescence) and fourier transform infrared spectroscopy (FTIR), circular dichroism spectroscopy (CD) and optical rotation polarimetry. It provided the necessary information on the secondary structure and the successful binding of copper(ii) to the specific amino acids, hence leading to the putative geometry of copper(ii)-peptides and the difference in the chirality of amino acids, peptides and copper(ii)-peptides. The catalytic activities of the synthesised complexes were evaluated. CuP1 & CuP3 catalysed both the asymmetric aldol reactions with high enantioselectivity of p-nitrobenzaldehyde with cyclohexanone (% ee = 87.3 & 80.3, respectively) and of p-anisaldehyde with cyclohexanone (% ee = 95.5 & 90.9, respectively). The Royal Society of Chemistry 2018-10-02 /pmc/articles/PMC9086720/ /pubmed/35548802 http://dx.doi.org/10.1039/c8ra06814c Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Sharifa Zaithun, Begum Emilia, AbdulMalek Mohamed Ibrahim Mohamed, Tahir Karen Anne, Crouse Mohd Basyaruddin, Abdul Rahman Histidine-based copper tetrapeptides as enantioselective catalysts for aldol reactions |
title | Histidine-based copper tetrapeptides as enantioselective catalysts for aldol reactions |
title_full | Histidine-based copper tetrapeptides as enantioselective catalysts for aldol reactions |
title_fullStr | Histidine-based copper tetrapeptides as enantioselective catalysts for aldol reactions |
title_full_unstemmed | Histidine-based copper tetrapeptides as enantioselective catalysts for aldol reactions |
title_short | Histidine-based copper tetrapeptides as enantioselective catalysts for aldol reactions |
title_sort | histidine-based copper tetrapeptides as enantioselective catalysts for aldol reactions |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9086720/ https://www.ncbi.nlm.nih.gov/pubmed/35548802 http://dx.doi.org/10.1039/c8ra06814c |
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