Biocatalytic Regioselective O‐acylation of Sesquiterpene Lactones from Chicory: A Pathway to Novel Ester Derivatives
Abstract We report the first biocatalytic modification of sesquiterpene lactones (STLs) found in the chicory plants, specifically lactucin (Lc), 11β , 13 ‐dihydrolactucin (DHLc), lactucopicrin (Lp), and 11β , 13 ‐dihydrolactucopicrin (DHLp). The selective O ‐acylation of their primary alcohol group...
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Online Access: | http://dx.doi.org/10.1002/cbic.202300722 |
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crwiley:10.1002/cbic.202300722 2024-06-02T07:57:25+00:00 Biocatalytic Regioselective O‐acylation of Sesquiterpene Lactones from Chicory: A Pathway to Novel Ester Derivatives Mosheim, J. Rodriguez Ruggieri, F. Humeau, C. Hance, P. Willand, N. Hilbert, J. L. Heuson, E. Froidevaux, R. Agence Nationale de la Recherche 2024 http://dx.doi.org/10.1002/cbic.202300722 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor ChemBioChem volume 25, issue 6 ISSN 1439-4227 1439-7633 journal-article 2024 crwiley https://doi.org/10.1002/cbic.202300722 2024-05-03T10:46:29Z Abstract We report the first biocatalytic modification of sesquiterpene lactones (STLs) found in the chicory plants, specifically lactucin (Lc), 11β , 13 ‐dihydrolactucin (DHLc), lactucopicrin (Lp), and 11β , 13 ‐dihydrolactucopicrin (DHLp). The selective O ‐acylation of their primary alcohol group was carried out by the lipase B from Candida antarctica (CAL ‐ B) using various aliphatic vinyl esters as acyl donors. Perillyl alcohol, a simpler monoterpenoid, served as a model to set up the desired O ‐acetylation reaction by comparing the use of acetic acid and vinyl acetate as acyl donors. Similar conditions were then applied to DHLc, where five novel ester chains were selectively introduced onto the primary alcohol group, with conversions going from >99 % (acetate and propionate) to 69 % (octanoate). The synthesis of the corresponding O ‐acetyl esters of Lc, Lp, and DHLp was also successfully achieved with near‐quantitative conversion. Molecular docking simulations were then performed to elucidate the preferred enzyme‐substrate binding modes in the acylation reactions with STLs, as well as to understand their interactions with crucial amino acid residues at the active site. Our methodology enables the selective O ‐acylation of the primary alcohol group in four different STLs, offering possibilities for synthesizing novel derivatives with significant potential applications in pharmaceuticals or as biocontrol agents. Article in Journal/Newspaper Antarc* Antarctica Wiley Online Library ChemBioChem |
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Open Polar |
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Wiley Online Library |
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crwiley |
language |
English |
description |
Abstract We report the first biocatalytic modification of sesquiterpene lactones (STLs) found in the chicory plants, specifically lactucin (Lc), 11β , 13 ‐dihydrolactucin (DHLc), lactucopicrin (Lp), and 11β , 13 ‐dihydrolactucopicrin (DHLp). The selective O ‐acylation of their primary alcohol group was carried out by the lipase B from Candida antarctica (CAL ‐ B) using various aliphatic vinyl esters as acyl donors. Perillyl alcohol, a simpler monoterpenoid, served as a model to set up the desired O ‐acetylation reaction by comparing the use of acetic acid and vinyl acetate as acyl donors. Similar conditions were then applied to DHLc, where five novel ester chains were selectively introduced onto the primary alcohol group, with conversions going from >99 % (acetate and propionate) to 69 % (octanoate). The synthesis of the corresponding O ‐acetyl esters of Lc, Lp, and DHLp was also successfully achieved with near‐quantitative conversion. Molecular docking simulations were then performed to elucidate the preferred enzyme‐substrate binding modes in the acylation reactions with STLs, as well as to understand their interactions with crucial amino acid residues at the active site. Our methodology enables the selective O ‐acylation of the primary alcohol group in four different STLs, offering possibilities for synthesizing novel derivatives with significant potential applications in pharmaceuticals or as biocontrol agents. |
author2 |
Agence Nationale de la Recherche |
format |
Article in Journal/Newspaper |
author |
Mosheim, J. Rodriguez Ruggieri, F. Humeau, C. Hance, P. Willand, N. Hilbert, J. L. Heuson, E. Froidevaux, R. |
spellingShingle |
Mosheim, J. Rodriguez Ruggieri, F. Humeau, C. Hance, P. Willand, N. Hilbert, J. L. Heuson, E. Froidevaux, R. Biocatalytic Regioselective O‐acylation of Sesquiterpene Lactones from Chicory: A Pathway to Novel Ester Derivatives |
author_facet |
Mosheim, J. Rodriguez Ruggieri, F. Humeau, C. Hance, P. Willand, N. Hilbert, J. L. Heuson, E. Froidevaux, R. |
author_sort |
Mosheim, J. Rodriguez |
title |
Biocatalytic Regioselective O‐acylation of Sesquiterpene Lactones from Chicory: A Pathway to Novel Ester Derivatives |
title_short |
Biocatalytic Regioselective O‐acylation of Sesquiterpene Lactones from Chicory: A Pathway to Novel Ester Derivatives |
title_full |
Biocatalytic Regioselective O‐acylation of Sesquiterpene Lactones from Chicory: A Pathway to Novel Ester Derivatives |
title_fullStr |
Biocatalytic Regioselective O‐acylation of Sesquiterpene Lactones from Chicory: A Pathway to Novel Ester Derivatives |
title_full_unstemmed |
Biocatalytic Regioselective O‐acylation of Sesquiterpene Lactones from Chicory: A Pathway to Novel Ester Derivatives |
title_sort |
biocatalytic regioselective o‐acylation of sesquiterpene lactones from chicory: a pathway to novel ester derivatives |
publisher |
Wiley |
publishDate |
2024 |
url |
http://dx.doi.org/10.1002/cbic.202300722 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
ChemBioChem volume 25, issue 6 ISSN 1439-4227 1439-7633 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/cbic.202300722 |
container_title |
ChemBioChem |
_version_ |
1800740580021501952 |