Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates †

A five-step transformation of a spiroketal side chain of tigogenin into an indolizidine system present in solanidane alkaloids such as demissidine and solanidine was elaborated. The key intermediate in the synthesis was spiroimine 3 readily obtained from tigogenin by its RuO(4) oxidation to 5,6-dihy...

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Autores principales: Wojtkielewicz, Agnieszka, Kiełczewska, Urszula, Baj, Aneta, Morzycki, Jacek W.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8509427/
https://www.ncbi.nlm.nih.gov/pubmed/34639219
http://dx.doi.org/10.3390/ijms221910879
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author Wojtkielewicz, Agnieszka
Kiełczewska, Urszula
Baj, Aneta
Morzycki, Jacek W.
author_facet Wojtkielewicz, Agnieszka
Kiełczewska, Urszula
Baj, Aneta
Morzycki, Jacek W.
author_sort Wojtkielewicz, Agnieszka
collection PubMed
description A five-step transformation of a spiroketal side chain of tigogenin into an indolizidine system present in solanidane alkaloids such as demissidine and solanidine was elaborated. The key intermediate in the synthesis was spiroimine 3 readily obtained from tigogenin by its RuO(4) oxidation to 5,6-dihydrokryptogenin followed by amination with aluminum amide generated in situ from DIBAlH and ammonium chloride. The mild reduction of spiroimine to a 26-hydroxy-dihydropyrrole derivative and subsequent mesylation resulted in the formation of 25-epidemissidinium salt or 23-sulfone depending on reaction conditions.
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spelling pubmed-85094272021-10-13 Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates † Wojtkielewicz, Agnieszka Kiełczewska, Urszula Baj, Aneta Morzycki, Jacek W. Int J Mol Sci Article A five-step transformation of a spiroketal side chain of tigogenin into an indolizidine system present in solanidane alkaloids such as demissidine and solanidine was elaborated. The key intermediate in the synthesis was spiroimine 3 readily obtained from tigogenin by its RuO(4) oxidation to 5,6-dihydrokryptogenin followed by amination with aluminum amide generated in situ from DIBAlH and ammonium chloride. The mild reduction of spiroimine to a 26-hydroxy-dihydropyrrole derivative and subsequent mesylation resulted in the formation of 25-epidemissidinium salt or 23-sulfone depending on reaction conditions. MDPI 2021-10-08 /pmc/articles/PMC8509427/ /pubmed/34639219 http://dx.doi.org/10.3390/ijms221910879 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Wojtkielewicz, Agnieszka
Kiełczewska, Urszula
Baj, Aneta
Morzycki, Jacek W.
Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates †
title Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates †
title_full Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates †
title_fullStr Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates †
title_full_unstemmed Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates †
title_short Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates †
title_sort synthesis of demissidine analogues from tigogenin via imine intermediates †
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8509427/
https://www.ncbi.nlm.nih.gov/pubmed/34639219
http://dx.doi.org/10.3390/ijms221910879
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