From secondary alcohols to tertiary fluoro substituents: A simple route to hydroxymethyl branched sugars with a fluorine substituent at the branching point

Michael Schalli; Martin Thonhofer; Andreas Wolfsgruber; Hansjörg Weber; Roland Fischer; Robert Saf; Arnold E Stütz

doi:10.1016/j.carres.2016.10.013

From secondary alcohols to tertiary fluoro substituents: A simple route to hydroxymethyl branched sugars with a fluorine substituent at the branching point

Carbohydr Res. 2016 Dec 21:436:11-19. doi: 10.1016/j.carres.2016.10.013. Epub 2016 Oct 29.

Authors

Michael Schalli¹, Martin Thonhofer¹, Andreas Wolfsgruber¹, Hansjörg Weber², Roland Fischer³, Robert Saf⁴, Arnold E Stütz⁵

Affiliations

¹ Glycogroup, Graz University of Technology, Stremayrgasse 9, A-8010, Graz, Austria.
² Institute for Organic Chemistry, Graz University of Technology, Stremayrgasse 9, A-8010, Graz, Austria.
³ Institute for Inorganic Chemistry, Graz University of Technology, Stremayrgasse 9, A-8010, Graz, Austria.
⁴ Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, A-8010, Graz, Austria.
⁵ Glycogroup, Graz University of Technology, Stremayrgasse 9, A-8010, Graz, Austria. Electronic address: [email protected].

PMID: 27829178
DOI: 10.1016/j.carres.2016.10.013

Abstract

From a secondary hydroxyl group, by the simple sequence of oxidation, Wittig reaction of the obtained ulose with methoxymethylene triphenyl phosphorane, exposure of the resulting exocyclic enol ether to Selectfluor and subsequent reduction of the α-fluoro aldehyde thus obtained, tertiary fluoro substituents can be introduced into carbohydrate and carbohydrate-related scaffolds at a branching point now bearing a new hydroxymethyl group.

Keywords: Branched-chain fluorosugar; Electrophilic fluorination; Selectfluor; Synthesis.

MeSH terms

Alcohols / chemistry*
Carbohydrates / chemistry*
Fluorides / chemistry*
Fluorine / chemistry*
Molecular Structure
Oxidation-Reduction
Stereoisomerism

Substances

Alcohols
Carbohydrates
Fluorine
Fluorides

Grants and funding

P 24815/FWF_/Austrian Science Fund FWF/Austria