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

Authors:Rubio Castillo, Enrique Miguel
García Moreno, María Isabel
Balbuena Olivia, Patricia
Lahoz, Fernando J.
Álvarez, Eleuterio
Ortiz-Mellet, Carmen
García-Fernández, José Manuel
Keywords:Acetals, Anhydrides, Fructose, Molecular conformation, Spiro compounds, Thermodynamics
Issue Date:18-Feb-2006
Publisher:American Chemical Society
Citation:Journal of Organic Chemistry 71(6): 2257-2266 (2006)
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 β-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.
Description:10 pages, 4 figures, 4 schemes.
Publisher version (URL):http://dx.doi.org/10.1021/jo052184b
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