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New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions

The preparation of new organocatalysts for asymmetric syntheses has become a key stage of enantioselective catalysis. In particular, the development of new cyclodextrin (CD)-based organocatalysts allowed to perform enantioselective reactions in water and to recycle catalysts. However, only a limited...

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Autores principales: Tichá, Iveta Chena, Hybelbauerová, Simona, Jindřich, Jindřich
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6466772/
https://www.ncbi.nlm.nih.gov/pubmed/31019575
http://dx.doi.org/10.3762/bjoc.15.80
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author Tichá, Iveta Chena
Hybelbauerová, Simona
Jindřich, Jindřich
author_facet Tichá, Iveta Chena
Hybelbauerová, Simona
Jindřich, Jindřich
author_sort Tichá, Iveta Chena
collection PubMed
description The preparation of new organocatalysts for asymmetric syntheses has become a key stage of enantioselective catalysis. In particular, the development of new cyclodextrin (CD)-based organocatalysts allowed to perform enantioselective reactions in water and to recycle catalysts. However, only a limited number of organocatalytic moieties and functional groups have been attached to CD scaffolds so far. Cinchona alkaloids are commonly used to catalyze a wide range of enantioselective reactions. Thus, in this study, we report the preparation of new α- and β-CD derivatives monosubstituted with cinchona alkaloids (cinchonine, cinchonidine, quinine and quinidine) on the primary rim through a CuAAC click reaction. Subsequently, permethylated analogs of these cinchona alkaloid–CD derivatives also were synthesized and the catalytic activity of all derivatives was evaluated in several enantioselective reactions, specifically in the asymmetric allylic amination (AAA), which showed a promising enantiomeric excess of up to 75% ee. Furthermore, a new disubstituted α-CD catalyst was prepared as a pure AD regioisomer and also tested in the AAA. Our results indicate that (i) the cinchona alkaloid moiety can be successfully attached to CD scaffolds through a CuAAC reaction, (ii) the permethylated cinchona alkaloid–CD catalysts showed better results than the non-methylated CDs analogues in the AAA reaction, (iii) promising enantiomeric excesses are achieved, and (iv) the disubstituted CD derivatives performed similarly to monosubstituted CDs. Therefore, these new CD derivatives with cinchona alkaloids effectively catalyze asymmetric allylic aminations and have the potential to be successfully applied in other enantioselective reactions.
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spelling pubmed-64667722019-04-24 New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions Tichá, Iveta Chena Hybelbauerová, Simona Jindřich, Jindřich Beilstein J Org Chem Full Research Paper The preparation of new organocatalysts for asymmetric syntheses has become a key stage of enantioselective catalysis. In particular, the development of new cyclodextrin (CD)-based organocatalysts allowed to perform enantioselective reactions in water and to recycle catalysts. However, only a limited number of organocatalytic moieties and functional groups have been attached to CD scaffolds so far. Cinchona alkaloids are commonly used to catalyze a wide range of enantioselective reactions. Thus, in this study, we report the preparation of new α- and β-CD derivatives monosubstituted with cinchona alkaloids (cinchonine, cinchonidine, quinine and quinidine) on the primary rim through a CuAAC click reaction. Subsequently, permethylated analogs of these cinchona alkaloid–CD derivatives also were synthesized and the catalytic activity of all derivatives was evaluated in several enantioselective reactions, specifically in the asymmetric allylic amination (AAA), which showed a promising enantiomeric excess of up to 75% ee. Furthermore, a new disubstituted α-CD catalyst was prepared as a pure AD regioisomer and also tested in the AAA. Our results indicate that (i) the cinchona alkaloid moiety can be successfully attached to CD scaffolds through a CuAAC reaction, (ii) the permethylated cinchona alkaloid–CD catalysts showed better results than the non-methylated CDs analogues in the AAA reaction, (iii) promising enantiomeric excesses are achieved, and (iv) the disubstituted CD derivatives performed similarly to monosubstituted CDs. Therefore, these new CD derivatives with cinchona alkaloids effectively catalyze asymmetric allylic aminations and have the potential to be successfully applied in other enantioselective reactions. Beilstein-Institut 2019-04-01 /pmc/articles/PMC6466772/ /pubmed/31019575 http://dx.doi.org/10.3762/bjoc.15.80 Text en Copyright © 2019, Tichá et al. https://creativecommons.org/licenses/by/4.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0). Please note that the reuse, redistribution and reproduction in particular requires that the authors and source are credited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms)
spellingShingle Full Research Paper
Tichá, Iveta Chena
Hybelbauerová, Simona
Jindřich, Jindřich
New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions
title New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions
title_full New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions
title_fullStr New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions
title_full_unstemmed New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions
title_short New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions
title_sort new α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6466772/
https://www.ncbi.nlm.nih.gov/pubmed/31019575
http://dx.doi.org/10.3762/bjoc.15.80
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