Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition

Sterically shielded nitroxides of the pyrrolidine series have shown the highest resistance to reduction. Here we report the synthesis of new pyrrolidine nitroxides from 5,5-dialkyl-1-pyrroline N-oxides via the introduction of a pent-4-enyl group to the nitrone carbon followed by an intramolecular 1,...

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Autores principales: Khoroshunova, Yulia V, Morozov, Denis A, Taratayko, Andrey I, Gladkikh, Polina D, Glazachev, Yuri I, Kirilyuk, Igor A
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2019
Materias:
Full Research Paper
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6720653/
https://www.ncbi.nlm.nih.gov/pubmed/31501671
http://dx.doi.org/10.3762/bjoc.15.200
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author Khoroshunova, Yulia V
Morozov, Denis A
Taratayko, Andrey I
Gladkikh, Polina D
Glazachev, Yuri I
Kirilyuk, Igor A
author_facet Khoroshunova, Yulia V
Morozov, Denis A
Taratayko, Andrey I
Gladkikh, Polina D
Glazachev, Yuri I
Kirilyuk, Igor A
author_sort Khoroshunova, Yulia V
collection PubMed
description Sterically shielded nitroxides of the pyrrolidine series have shown the highest resistance to reduction. Here we report the synthesis of new pyrrolidine nitroxides from 5,5-dialkyl-1-pyrroline N-oxides via the introduction of a pent-4-enyl group to the nitrone carbon followed by an intramolecular 1,3-dipolar cycloaddition reaction and isoxazolidine ring opening. The kinetics of reduction of the new nitroxides with ascorbate were studied and compared to those of previously published (1S,2R,3′S,4′S,5′S,2″R)-dispiro[(2-hydroxymethyl)cyclopentan-1,2′-(3′,4′-di-tert-butoxy)pyrrolidine-5′,1″-(2″-hydroxymethyl)cyclopentane]-1′-oxyl (1).
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spelling pubmed-67206532019-09-09 Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition Khoroshunova, Yulia V Morozov, Denis A Taratayko, Andrey I Gladkikh, Polina D Glazachev, Yuri I Kirilyuk, Igor A Beilstein J Org Chem Full Research Paper Sterically shielded nitroxides of the pyrrolidine series have shown the highest resistance to reduction. Here we report the synthesis of new pyrrolidine nitroxides from 5,5-dialkyl-1-pyrroline N-oxides via the introduction of a pent-4-enyl group to the nitrone carbon followed by an intramolecular 1,3-dipolar cycloaddition reaction and isoxazolidine ring opening. The kinetics of reduction of the new nitroxides with ascorbate were studied and compared to those of previously published (1S,2R,3′S,4′S,5′S,2″R)-dispiro[(2-hydroxymethyl)cyclopentan-1,2′-(3′,4′-di-tert-butoxy)pyrrolidine-5′,1″-(2″-hydroxymethyl)cyclopentane]-1′-oxyl (1). Beilstein-Institut 2019-08-27 /pmc/articles/PMC6720653/ /pubmed/31501671 http://dx.doi.org/10.3762/bjoc.15.200 Text en Copyright © 2019, Khoroshunova 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
Khoroshunova, Yulia V
Morozov, Denis A
Taratayko, Andrey I
Gladkikh, Polina D
Glazachev, Yuri I
Kirilyuk, Igor A
Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition
title Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition
title_full Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition
title_fullStr Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition
title_full_unstemmed Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition
title_short Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition
title_sort synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6720653/
https://www.ncbi.nlm.nih.gov/pubmed/31501671
http://dx.doi.org/10.3762/bjoc.15.200
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