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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...

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Autores principales: Biondi, Daniela Maria, Sanfilippo, Claudia, Patti, Angela
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
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.
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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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