Stereoselective Synthesis of γ‐(Acyloxy)carboxylic Acids and γ‐Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ‐Hydroxycarboxylate Homologues
Abstract Scalable protocols of straightforward synthesis of enantiomeric γ‐(acyloxy)carboxylic acids and γ‐lactones are presented. The key step is lipase‐catalyzed stereoselective acylation of γ‐hydroxycarboxylic acid sodium salt in organic solvent followed by acidification of the product, extractio...
Published in: | European Journal of Organic Chemistry |
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Online Access: | http://dx.doi.org/10.1002/ejoc.202201329 https://onlinelibrary.wiley.com/doi/pdf/10.1002/ejoc.202201329 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ejoc.202201329 |
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crwiley:10.1002/ejoc.202201329 2024-06-02T07:58:40+00:00 Stereoselective Synthesis of γ‐(Acyloxy)carboxylic Acids and γ‐Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ‐Hydroxycarboxylate Homologues Parve, Jaan Kudryashova, Marina Shalima, Tatsiana Villo, Ly Ferschel, Moonika Niidu, Allan Liblikas, Ilme Reile, Indrek Aav, Riina Gathergood, Nicholas Vares, Lauri Pehk, Tõnis Parve, Omar Eesti Teadusagentuur European Regional Development Fund 2022 http://dx.doi.org/10.1002/ejoc.202201329 https://onlinelibrary.wiley.com/doi/pdf/10.1002/ejoc.202201329 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ejoc.202201329 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor European Journal of Organic Chemistry volume 26, issue 3 ISSN 1434-193X 1099-0690 journal-article 2022 crwiley https://doi.org/10.1002/ejoc.202201329 2024-05-03T12:07:24Z Abstract Scalable protocols of straightforward synthesis of enantiomeric γ‐(acyloxy)carboxylic acids and γ‐lactones are presented. The key step is lipase‐catalyzed stereoselective acylation of γ‐hydroxycarboxylic acid sodium salt in organic solvent followed by acidification of the product, extraction and acidic relactonization of the unreacted enantiomer. The mixture of γ‐(acyloxy)carboxylic acid and γ‐lactone is separated either by extraction with solution of sodium bicarbonate or by distillation. A switch of enantioinduction of Candida antarctica lipase B along homologous nucleophiles from R configuration of γ‐hydroxyhexanoic acid salt to S configuration of the C7 and longer‐chain homologues has been disclosed. Both enantiomers of γ‐(acyloxy)pentanoic acids; γ‐(acetyloxy)octanoic and ‐nonanoic acids with S configuration; [(1 S ,5 R )‐5‐(chloroacetyloxy)cyclopent‐2‐en‐1‐yl]acetic acid and enantiomeric γ‐lactones derived from them were prepared with e. r . >98.5/1.5. The rates of acylation of C5 to C9 homologous salts differ by three orders of magnitude but remain applicable for preparative synthesis by variation of the enzyme loading and reaction time. Article in Journal/Newspaper Antarc* Antarctica Wiley Online Library European Journal of Organic Chemistry 26 3 |
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Wiley Online Library |
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crwiley |
language |
English |
description |
Abstract Scalable protocols of straightforward synthesis of enantiomeric γ‐(acyloxy)carboxylic acids and γ‐lactones are presented. The key step is lipase‐catalyzed stereoselective acylation of γ‐hydroxycarboxylic acid sodium salt in organic solvent followed by acidification of the product, extraction and acidic relactonization of the unreacted enantiomer. The mixture of γ‐(acyloxy)carboxylic acid and γ‐lactone is separated either by extraction with solution of sodium bicarbonate or by distillation. A switch of enantioinduction of Candida antarctica lipase B along homologous nucleophiles from R configuration of γ‐hydroxyhexanoic acid salt to S configuration of the C7 and longer‐chain homologues has been disclosed. Both enantiomers of γ‐(acyloxy)pentanoic acids; γ‐(acetyloxy)octanoic and ‐nonanoic acids with S configuration; [(1 S ,5 R )‐5‐(chloroacetyloxy)cyclopent‐2‐en‐1‐yl]acetic acid and enantiomeric γ‐lactones derived from them were prepared with e. r . >98.5/1.5. The rates of acylation of C5 to C9 homologous salts differ by three orders of magnitude but remain applicable for preparative synthesis by variation of the enzyme loading and reaction time. |
author2 |
Eesti Teadusagentuur European Regional Development Fund |
format |
Article in Journal/Newspaper |
author |
Parve, Jaan Kudryashova, Marina Shalima, Tatsiana Villo, Ly Ferschel, Moonika Niidu, Allan Liblikas, Ilme Reile, Indrek Aav, Riina Gathergood, Nicholas Vares, Lauri Pehk, Tõnis Parve, Omar |
spellingShingle |
Parve, Jaan Kudryashova, Marina Shalima, Tatsiana Villo, Ly Ferschel, Moonika Niidu, Allan Liblikas, Ilme Reile, Indrek Aav, Riina Gathergood, Nicholas Vares, Lauri Pehk, Tõnis Parve, Omar Stereoselective Synthesis of γ‐(Acyloxy)carboxylic Acids and γ‐Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ‐Hydroxycarboxylate Homologues |
author_facet |
Parve, Jaan Kudryashova, Marina Shalima, Tatsiana Villo, Ly Ferschel, Moonika Niidu, Allan Liblikas, Ilme Reile, Indrek Aav, Riina Gathergood, Nicholas Vares, Lauri Pehk, Tõnis Parve, Omar |
author_sort |
Parve, Jaan |
title |
Stereoselective Synthesis of γ‐(Acyloxy)carboxylic Acids and γ‐Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ‐Hydroxycarboxylate Homologues |
title_short |
Stereoselective Synthesis of γ‐(Acyloxy)carboxylic Acids and γ‐Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ‐Hydroxycarboxylate Homologues |
title_full |
Stereoselective Synthesis of γ‐(Acyloxy)carboxylic Acids and γ‐Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ‐Hydroxycarboxylate Homologues |
title_fullStr |
Stereoselective Synthesis of γ‐(Acyloxy)carboxylic Acids and γ‐Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ‐Hydroxycarboxylate Homologues |
title_full_unstemmed |
Stereoselective Synthesis of γ‐(Acyloxy)carboxylic Acids and γ‐Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ‐Hydroxycarboxylate Homologues |
title_sort |
stereoselective synthesis of γ‐(acyloxy)carboxylic acids and γ‐lactones featuring the switch of stereopreference of candida antarctica lipase b in sodium γ‐hydroxycarboxylate homologues |
publisher |
Wiley |
publishDate |
2022 |
url |
http://dx.doi.org/10.1002/ejoc.202201329 https://onlinelibrary.wiley.com/doi/pdf/10.1002/ejoc.202201329 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ejoc.202201329 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
European Journal of Organic Chemistry volume 26, issue 3 ISSN 1434-193X 1099-0690 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/ejoc.202201329 |
container_title |
European Journal of Organic Chemistry |
container_volume |
26 |
container_issue |
3 |
_version_ |
1800742105448972288 |