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Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds
Limonene is one of the most abundant naturally occurring cyclic monoterpenes and has recently emerged as a sustainable alternative to petroleum-based solvents as well as a chemical platform for the production of value-added compounds. The biocatalytic epoxidation of both enantiomers of limonene was...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8469233/ https://www.ncbi.nlm.nih.gov/pubmed/34573093 http://dx.doi.org/10.3390/antiox10091462 |
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author | Biondi, Daniela Maria Sanfilippo, Claudia Patti, Angela |
author_facet | Biondi, Daniela Maria Sanfilippo, Claudia Patti, Angela |
author_sort | Biondi, Daniela Maria |
collection | PubMed |
description | Limonene is one of the most abundant naturally occurring cyclic monoterpenes and has recently emerged as a sustainable alternative to petroleum-based solvents as well as a chemical platform for the production of value-added compounds. The biocatalytic epoxidation of both enantiomers of limonene was carried out in the presence of a peroxygenase-containing preparation from oat (Avena sativa) flour. Different reaction profiles were observed depending on the starting enantiomer of limonene, but in both cases the 1,2-monoepoxide was obtained as the main product with excellent diastereoselectivity. Trans-1,2-monoepoxide and cis-1,2-monoepoxide were isolated from the reaction of (R)-limonene and (S)-limonene, respectively, and the reactions were scaled-up to 0.17 M substrate concentration. The process is valuable for operational simplicity, lack of toxic metal catalysts, and cost-effectiveness of the enzymatic source. Pure stereoisomers of 1,2-monoepoxides of limonene constitute a useful starting material for biorenewable polymers, but can be also converted into other chiral derivatives by epoxide ring opening with nucleophiles. As a proof of concept, a tandem protocol for the preparation of enantiopure (1S,2S,4R)-1,2-diol from (R)-limonene and (1R,2R,4S)-1,2-diol from (S)-limonene was developed. |
format | Online Article Text |
id | pubmed-8469233 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-84692332021-09-27 Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds Biondi, Daniela Maria Sanfilippo, Claudia Patti, Angela Antioxidants (Basel) Article Limonene is one of the most abundant naturally occurring cyclic monoterpenes and has recently emerged as a sustainable alternative to petroleum-based solvents as well as a chemical platform for the production of value-added compounds. The biocatalytic epoxidation of both enantiomers of limonene was carried out in the presence of a peroxygenase-containing preparation from oat (Avena sativa) flour. Different reaction profiles were observed depending on the starting enantiomer of limonene, but in both cases the 1,2-monoepoxide was obtained as the main product with excellent diastereoselectivity. Trans-1,2-monoepoxide and cis-1,2-monoepoxide were isolated from the reaction of (R)-limonene and (S)-limonene, respectively, and the reactions were scaled-up to 0.17 M substrate concentration. The process is valuable for operational simplicity, lack of toxic metal catalysts, and cost-effectiveness of the enzymatic source. Pure stereoisomers of 1,2-monoepoxides of limonene constitute a useful starting material for biorenewable polymers, but can be also converted into other chiral derivatives by epoxide ring opening with nucleophiles. As a proof of concept, a tandem protocol for the preparation of enantiopure (1S,2S,4R)-1,2-diol from (R)-limonene and (1R,2R,4S)-1,2-diol from (S)-limonene was developed. MDPI 2021-09-14 /pmc/articles/PMC8469233/ /pubmed/34573093 http://dx.doi.org/10.3390/antiox10091462 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Biondi, Daniela Maria Sanfilippo, Claudia Patti, Angela Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds |
title | Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds |
title_full | Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds |
title_fullStr | Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds |
title_full_unstemmed | Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds |
title_short | Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds |
title_sort | stereospecific epoxidation of limonene catalyzed by peroxygenase from oat seeds |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8469233/ https://www.ncbi.nlm.nih.gov/pubmed/34573093 http://dx.doi.org/10.3390/antiox10091462 |
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