Chemo-Enzymatic Synthesis of Chiral Epoxides Ethyl and Methyl (S)-3-(Oxiran-2-yl)propanoates from Renewable Levoglucosenone: An Access to Enantiopure (S)-Dairy Lactone.
Identifieur interne : 002234 ( Main/Exploration ); précédent : 002233; suivant : 002235Chemo-Enzymatic Synthesis of Chiral Epoxides Ethyl and Methyl (S)-3-(Oxiran-2-yl)propanoates from Renewable Levoglucosenone: An Access to Enantiopure (S)-Dairy Lactone.
Auteurs : Aurélien A M. Peru [France] ; Amandine L. Flourat [France] ; Christian Gunawan [Australie] ; Warwick Raverty [Australie] ; Martyn Jevric [Australie] ; Ben W. Greatrex [Australie] ; Florent Allais [France]Source :
- Molecules (Basel, Switzerland) [ 1420-3049 ] ; 2016.
Descripteurs français
- KwdFr :
- MESH :
- analogues et dérivés : Glucose.
- synthèse chimique : Composés époxy, Propionates.
- Composés hétérocycliques bicycliques, Composés époxy, Glucose, Lactones, Propionates.
English descriptors
- KwdEn :
- MESH :
- chemical , analogs & derivatives : Glucose.
- chemical , chemical synthesis : Epoxy Compounds, Propionates.
- chemical , chemistry : Bridged Bicyclo Compounds, Heterocyclic, Epoxy Compounds, Glucose, Lactones, Propionates.
Abstract
Chiral epoxides-such as ethyl and methyl (S)-3-(oxiran-2-yl)propanoates ((S)-1a/1b)-are valuable precursors in many chemical syntheses. Until recently, these compounds were synthesized from glutamic acid in four steps (deamination, reduction, tosylation and epoxide formation) in low to moderate overall yield (20%-50%). Moreover, this procedure requires some harmful reagents such as sodium nitrite ((eco)toxic) and borane (carcinogen). Herein, starting from levoglucosenone (LGO), a biobased chiral compound obtained through the flash pyrolysis of acidified cellulose, we propose a safer and more sustainable chemo-enzymatic synthetic pathway involving lipase-mediated Baeyer-Villiger oxidation, palladium-catalyzed hydrogenation, tosylation and treatment with sodium ethoxide/methoxide as key steps. This route afforded ethyl and methyl (S)-3-(oxiran-2-yl)propanoates in 57% overall yield, respectively. To demonstrate the potentiality of this new synthetic pathway from LGO, the synthesis of high value-added (S)-dairy lactone was undertaken from these epoxides and provided the target in 37% overall yield from LGO.
DOI: 10.3390/molecules21080988
PubMed: 27483225
Affiliations:
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Peru</name><affiliation wicri:level="3"><nlm:affiliation>Chaire ABI-AgroParisTech, CEBB, 3 rue des Rouges Terres, 51110 Pomacle, France. florent.allais@agroparistech.fr.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Chaire ABI-AgroParisTech, CEBB, 3 rue des Rouges Terres, 51110 Pomacle</wicri:regionArea><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Champagne-Ardenne</region><settlement type="city">Pomacle</settlement></placeName></affiliation></author><author><name sortKey="Flourat, Amandine L" sort="Flourat, Amandine L" uniqKey="Flourat A" first="Amandine L" last="Flourat">Amandine L. 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Until recently, these compounds were synthesized from glutamic acid in four steps (deamination, reduction, tosylation and epoxide formation) in low to moderate overall yield (20%-50%). Moreover, this procedure requires some harmful reagents such as sodium nitrite ((eco)toxic) and borane (carcinogen). Herein, starting from levoglucosenone (LGO), a biobased chiral compound obtained through the flash pyrolysis of acidified cellulose, we propose a safer and more sustainable chemo-enzymatic synthetic pathway involving lipase-mediated Baeyer-Villiger oxidation, palladium-catalyzed hydrogenation, tosylation and treatment with sodium ethoxide/methoxide as key steps. This route afforded ethyl and methyl (S)-3-(oxiran-2-yl)propanoates in 57% overall yield, respectively. To demonstrate the potentiality of this new synthetic pathway from LGO, the synthesis of high value-added (S)-dairy lactone was undertaken from these epoxides and provided the target in 37% overall yield from LGO.</div></front></TEI><affiliations><list><country><li>Australie</li><li>France</li></country><region><li>Champagne-Ardenne</li><li>Grand Est</li></region><settlement><li>Pomacle</li></settlement></list><tree><country name="France"><region name="Grand Est"><name sortKey="Peru, Aurelien A M" sort="Peru, Aurelien A M" uniqKey="Peru A" first="Aurélien A M" last="Peru">Aurélien A M. Peru</name></region><name sortKey="Allais, Florent" sort="Allais, Florent" uniqKey="Allais F" first="Florent" last="Allais">Florent Allais</name><name sortKey="Flourat, Amandine L" sort="Flourat, Amandine L" uniqKey="Flourat A" first="Amandine L" last="Flourat">Amandine L. Flourat</name></country><country name="Australie"><noRegion><name sortKey="Gunawan, Christian" sort="Gunawan, Christian" uniqKey="Gunawan C" first="Christian" last="Gunawan">Christian Gunawan</name></noRegion><name sortKey="Greatrex, Ben W" sort="Greatrex, Ben W" uniqKey="Greatrex B" first="Ben W" last="Greatrex">Ben W. Greatrex</name><name sortKey="Jevric, Martyn" sort="Jevric, Martyn" uniqKey="Jevric M" first="Martyn" last="Jevric">Martyn Jevric</name><name sortKey="Raverty, Warwick" sort="Raverty, Warwick" uniqKey="Raverty W" first="Warwick" last="Raverty">Warwick Raverty</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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