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Regio- and stereoselective synthesis of new diaminocyclopentanols

The optimal conditions for regio- and stereoselective epoxide ring opening of N,N-disubstituted 1,2-epoxy-3-aminocyclopentanes by different nucleophilic reagents have been developed. The substituents on the nitrogen atom in the epoxide precursor and the orientation of the oxirane ring are crucial fo...

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Autores principales: Larin, Evgeni A, Kochubei, Valeri S, Atroshchenko, Yuri M
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2014
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4222406/
https://www.ncbi.nlm.nih.gov/pubmed/25383122
http://dx.doi.org/10.3762/bjoc.10.262
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author Larin, Evgeni A
Kochubei, Valeri S
Atroshchenko, Yuri M
author_facet Larin, Evgeni A
Kochubei, Valeri S
Atroshchenko, Yuri M
author_sort Larin, Evgeni A
collection PubMed
description The optimal conditions for regio- and stereoselective epoxide ring opening of N,N-disubstituted 1,2-epoxy-3-aminocyclopentanes by different nucleophilic reagents have been developed. The substituents on the nitrogen atom in the epoxide precursor and the orientation of the oxirane ring are crucial for the reaction outcome. Thus, treatment of (1RS,2SR,3SR)-1,2-epoxy-3-(N,N-dibenzylamino)cyclopentane (3b) with amines gave a mixture of C1 and C2 regioadducts, while the use of (1RS,2SR,3SR)-1,2-epoxy-3-(N-benzyl-N-methylamino)cyclopentane (3a) led ultimately to C1 adducts. Base-catalyzed aminolysis of epoxides 6a,b afforded mainly C1 adducts 13a,b arising from trans-diaxal opening of the epoxide ring. Using a Lewis acid catalyst, epoxides 6a,b were transformed into diaminocyclopentanols 14a,b via an alternative pathway involving the formation of aziridinium intermediate 17.
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spelling pubmed-42224062014-11-07 Regio- and stereoselective synthesis of new diaminocyclopentanols Larin, Evgeni A Kochubei, Valeri S Atroshchenko, Yuri M Beilstein J Org Chem Full Research Paper The optimal conditions for regio- and stereoselective epoxide ring opening of N,N-disubstituted 1,2-epoxy-3-aminocyclopentanes by different nucleophilic reagents have been developed. The substituents on the nitrogen atom in the epoxide precursor and the orientation of the oxirane ring are crucial for the reaction outcome. Thus, treatment of (1RS,2SR,3SR)-1,2-epoxy-3-(N,N-dibenzylamino)cyclopentane (3b) with amines gave a mixture of C1 and C2 regioadducts, while the use of (1RS,2SR,3SR)-1,2-epoxy-3-(N-benzyl-N-methylamino)cyclopentane (3a) led ultimately to C1 adducts. Base-catalyzed aminolysis of epoxides 6a,b afforded mainly C1 adducts 13a,b arising from trans-diaxal opening of the epoxide ring. Using a Lewis acid catalyst, epoxides 6a,b were transformed into diaminocyclopentanols 14a,b via an alternative pathway involving the formation of aziridinium intermediate 17. Beilstein-Institut 2014-10-28 /pmc/articles/PMC4222406/ /pubmed/25383122 http://dx.doi.org/10.3762/bjoc.10.262 Text en Copyright © 2014, Larin et al. https://creativecommons.org/licenses/by/2.0https://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/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. 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
Larin, Evgeni A
Kochubei, Valeri S
Atroshchenko, Yuri M
Regio- and stereoselective synthesis of new diaminocyclopentanols
title Regio- and stereoselective synthesis of new diaminocyclopentanols
title_full Regio- and stereoselective synthesis of new diaminocyclopentanols
title_fullStr Regio- and stereoselective synthesis of new diaminocyclopentanols
title_full_unstemmed Regio- and stereoselective synthesis of new diaminocyclopentanols
title_short Regio- and stereoselective synthesis of new diaminocyclopentanols
title_sort regio- and stereoselective synthesis of new diaminocyclopentanols
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4222406/
https://www.ncbi.nlm.nih.gov/pubmed/25383122
http://dx.doi.org/10.3762/bjoc.10.262
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