Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates

Addition of carboxylic acid dianions appears to be a potential alternative to the use of aluminium enolates for nucleophilic ring opening of epoxides. These conditions require the use of a sub-stoichiometric amount of amine (10% mol) for dianion generation and the previous activation of the epoxide...

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Main Authors: José Segura, Margarita Parra, Salvador Gil, Luis R. Domingo
Format: Article
Language:English
Published: MDPI AG 2008-06-01
Series:Molecules
Subjects:
Online Access:http://www.mdpi.com/1420-3049/13/6/1303/
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author José Segura
Margarita Parra
Salvador Gil
Luis R. Domingo
author_facet José Segura
Margarita Parra
Salvador Gil
Luis R. Domingo
author_sort José Segura
collection DOAJ
description Addition of carboxylic acid dianions appears to be a potential alternative to the use of aluminium enolates for nucleophilic ring opening of epoxides. These conditions require the use of a sub-stoichiometric amount of amine (10% mol) for dianion generation and the previous activation of the epoxide with LiCl. Yields are good, with high regioselectivity, but the use of styrene oxide led, unexpectedly, to a mixture resulting from the attack on both the primary and secondary carbon atoms. Generally, a low diastereoselectivity is seen on attack at the primary center, however only one diastereoisomer was obtained from attack to the secondary carbon of the styrene oxide.
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spelling doaj.art-1285d7b7838542388db3b6d8457bfd412022-12-22T01:26:05ZengMDPI AGMolecules1420-30492008-06-011361303131110.3390/molecules13061303Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid EnediolatesJosé SeguraMargarita ParraSalvador GilLuis R. DomingoAddition of carboxylic acid dianions appears to be a potential alternative to the use of aluminium enolates for nucleophilic ring opening of epoxides. These conditions require the use of a sub-stoichiometric amount of amine (10% mol) for dianion generation and the previous activation of the epoxide with LiCl. Yields are good, with high regioselectivity, but the use of styrene oxide led, unexpectedly, to a mixture resulting from the attack on both the primary and secondary carbon atoms. Generally, a low diastereoselectivity is seen on attack at the primary center, however only one diastereoisomer was obtained from attack to the secondary carbon of the styrene oxide.http://www.mdpi.com/1420-3049/13/6/1303/Lactoneslithium chloridenucleophilic additionregioselectivitydiastereoselectivity.
spellingShingle José Segura
Margarita Parra
Salvador Gil
Luis R. Domingo
Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates
Molecules
Lactones
lithium chloride
nucleophilic addition
regioselectivity
diastereoselectivity.
title Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates
title_full Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates
title_fullStr Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates
title_full_unstemmed Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates
title_short Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates
title_sort unusual regioselectivity in the opening of epoxides by carboxylic acid enediolates
topic Lactones
lithium chloride
nucleophilic addition
regioselectivity
diastereoselectivity.
url http://www.mdpi.com/1420-3049/13/6/1303/
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