Spacer-mediated synthesis of contra-thermodynamic spiroacetals: stereoselective synthesis of C2-symmetric difructose dianhydrides

The Journal of Organic Chemistry
Enrique M RubioJosé M García Fernández

Abstract

The xylylene moiety (ortho, meta, and para) was employed as a rigid tether in the spacer-mediated synthesis of difructose dianhydrides (DFAs), a unique class of bis-spiroacetal derivatives present in food products. The synthetic methodology exploits the suitability of triflic acid to promote spirocyclization in organic solvents under irreversible reaction conditions, using anomeric isopropylidene fructose derivatives as precursors. Advantage was taken of the strong dependence of the conformational properties of DFAs on the relative configuration of the spiroketal centers. Highly stereoselective syntheses of the contra-thermodynamic difructofuranose and difructopyranose diastereomers, namely the C2-symmetric derivatives having the beta-configuration at both anomeric centers, have been accomplished by judicious choice of the xylylene positional isomer and of the linking position to the fructose building blocks. Interestingly, the rigid spacer concept has also been implemented to favor intermolecular processes leading to higher macrocyclic architectures that incorporate the bis-spiro fructodisaccharide subunit.

References

Apr 1, 1994·Carbohydrate Research·J Defaye, J M García Fernández
Jun 21, 1996·Carbohydrate Research·M Manley-Harris, G N Richards
May 23, 2000·Journal of Agricultural and Food Chemistry·T J ChristianB A Parker
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Citations

Jun 17, 2006·Chemical Communications : Chem Comm·Patricia BalbuenaJosé M García Fernández
May 31, 2017·Journal of Agricultural and Food Chemistry·Maïté AudemarKarine De Oliveira Vigier
Sep 23, 2006·Organic & Biomolecular Chemistry·Hideya YuasaHironobu Hashimoto
Sep 17, 2008·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·M Isabel García-MorenoJosé M García Fernández
Oct 11, 2016·Nanoscale·Lawrence A CrosbyLaurence D Marks
Dec 31, 2009·Journal of Agricultural and Food Chemistry·Elena Suárez-PereiraJosé M García Fernández

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