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Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars

Higher aminosugars are interesting targets in carbohydrate synthesis since these compounds play important roles in biological systems. However, their availability from natural sources is limited. Thus, in order to investigate their biological function, the development of facile and adaptable routes...

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Autores principales: Albler, Christopher, Hollaus, Ralph, Kählig, Hanspeter, Schmid, Walther
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2014
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4168925/
https://www.ncbi.nlm.nih.gov/pubmed/25246982
http://dx.doi.org/10.3762/bjoc.10.231
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author Albler, Christopher
Hollaus, Ralph
Kählig, Hanspeter
Schmid, Walther
author_facet Albler, Christopher
Hollaus, Ralph
Kählig, Hanspeter
Schmid, Walther
author_sort Albler, Christopher
collection PubMed
description Higher aminosugars are interesting targets in carbohydrate synthesis since these compounds play important roles in biological systems. However, their availability from natural sources is limited. Thus, in order to investigate their biological function, the development of facile and adaptable routes to this class of compounds is of fundamental importance. Our synthetic route towards these target molecules makes use of readily accessible pentoses and hexoses, which are subjected to indium-mediated two-carbon chain elongation. Subsequent ozonolysis and treatment with base yields α,β-unsaturated aldehydes, which are stereoselectively epoxidized using Jørgenson’s protocol. After Wittig chain elongation the obtained allylic epoxides were regio- and stereoselectively opened with trimethylsilyl azide under palladium catalysis. Finally, a suitable deprotection protocol, starting with acidic acetate cleavage and ozonolysis was established. Peracetylation of the products simplifies purification and subsequent azide reduction followed by final deacetylation using methanolic sodium methoxide furnishes the title compounds.
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spelling pubmed-41689252014-09-22 Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars Albler, Christopher Hollaus, Ralph Kählig, Hanspeter Schmid, Walther Beilstein J Org Chem Full Research Paper Higher aminosugars are interesting targets in carbohydrate synthesis since these compounds play important roles in biological systems. However, their availability from natural sources is limited. Thus, in order to investigate their biological function, the development of facile and adaptable routes to this class of compounds is of fundamental importance. Our synthetic route towards these target molecules makes use of readily accessible pentoses and hexoses, which are subjected to indium-mediated two-carbon chain elongation. Subsequent ozonolysis and treatment with base yields α,β-unsaturated aldehydes, which are stereoselectively epoxidized using Jørgenson’s protocol. After Wittig chain elongation the obtained allylic epoxides were regio- and stereoselectively opened with trimethylsilyl azide under palladium catalysis. Finally, a suitable deprotection protocol, starting with acidic acetate cleavage and ozonolysis was established. Peracetylation of the products simplifies purification and subsequent azide reduction followed by final deacetylation using methanolic sodium methoxide furnishes the title compounds. Beilstein-Institut 2014-09-19 /pmc/articles/PMC4168925/ /pubmed/25246982 http://dx.doi.org/10.3762/bjoc.10.231 Text en Copyright © 2014, Albler 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
Albler, Christopher
Hollaus, Ralph
Kählig, Hanspeter
Schmid, Walther
Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars
title Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars
title_full Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars
title_fullStr Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars
title_full_unstemmed Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars
title_short Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars
title_sort indium-mediated allylation in carbohydrate synthesis: a short and efficient approach towards higher 2-acetamido-2-deoxy sugars
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4168925/
https://www.ncbi.nlm.nih.gov/pubmed/25246982
http://dx.doi.org/10.3762/bjoc.10.231
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