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Glycosyl Dithiocarbamates: β-Selective Couplings without Auxiliary Groups

[Image: see text] In this article, we evaluate glycosyl dithiocarbamates (DTCs) with unprotected C2 hydroxyls as donors in β-linked oligosaccharide synthesis. We report a mild, one-pot conversion of glycals into β-glycosyl DTCs via DMDO oxidation with subsequent ring opening by DTC salts, which can...

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Autores principales: Padungros, Panuwat, Alberch, Laura, Wei, Alexander
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3985838/
https://www.ncbi.nlm.nih.gov/pubmed/24548247
http://dx.doi.org/10.1021/jo500032k
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author Padungros, Panuwat
Alberch, Laura
Wei, Alexander
author_facet Padungros, Panuwat
Alberch, Laura
Wei, Alexander
author_sort Padungros, Panuwat
collection PubMed
description [Image: see text] In this article, we evaluate glycosyl dithiocarbamates (DTCs) with unprotected C2 hydroxyls as donors in β-linked oligosaccharide synthesis. We report a mild, one-pot conversion of glycals into β-glycosyl DTCs via DMDO oxidation with subsequent ring opening by DTC salts, which can be generated in situ from secondary amines and CS(2). Glycosyl DTCs are readily activated with Cu(I) or Cu(II) triflate at low temperatures and are amenable to reiterative synthesis strategies, as demonstrated by the efficient construction of a tri-β-1,6-linked tetrasaccharide. Glycosyl DTC couplings are highly β-selective despite the absence of a preexisting C2 auxiliary group. We provide evidence that the directing effect is mediated by the C2 hydroxyl itself via the putative formation of a cis-fused bicyclic intermediate.
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spelling pubmed-39858382015-02-18 Glycosyl Dithiocarbamates: β-Selective Couplings without Auxiliary Groups Padungros, Panuwat Alberch, Laura Wei, Alexander J Org Chem [Image: see text] In this article, we evaluate glycosyl dithiocarbamates (DTCs) with unprotected C2 hydroxyls as donors in β-linked oligosaccharide synthesis. We report a mild, one-pot conversion of glycals into β-glycosyl DTCs via DMDO oxidation with subsequent ring opening by DTC salts, which can be generated in situ from secondary amines and CS(2). Glycosyl DTCs are readily activated with Cu(I) or Cu(II) triflate at low temperatures and are amenable to reiterative synthesis strategies, as demonstrated by the efficient construction of a tri-β-1,6-linked tetrasaccharide. Glycosyl DTC couplings are highly β-selective despite the absence of a preexisting C2 auxiliary group. We provide evidence that the directing effect is mediated by the C2 hydroxyl itself via the putative formation of a cis-fused bicyclic intermediate. American Chemical Society 2014-02-18 2014-03-21 /pmc/articles/PMC3985838/ /pubmed/24548247 http://dx.doi.org/10.1021/jo500032k Text en Copyright © 2014 American Chemical Society
spellingShingle Padungros, Panuwat
Alberch, Laura
Wei, Alexander
Glycosyl Dithiocarbamates: β-Selective Couplings without Auxiliary Groups
title Glycosyl Dithiocarbamates: β-Selective Couplings without Auxiliary Groups
title_full Glycosyl Dithiocarbamates: β-Selective Couplings without Auxiliary Groups
title_fullStr Glycosyl Dithiocarbamates: β-Selective Couplings without Auxiliary Groups
title_full_unstemmed Glycosyl Dithiocarbamates: β-Selective Couplings without Auxiliary Groups
title_short Glycosyl Dithiocarbamates: β-Selective Couplings without Auxiliary Groups
title_sort glycosyl dithiocarbamates: β-selective couplings without auxiliary groups
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3985838/
https://www.ncbi.nlm.nih.gov/pubmed/24548247
http://dx.doi.org/10.1021/jo500032k
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