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High-throughput Synthesis of Carbohydrates and Functionalization of Polyanhydride Nanoparticles
Published on: July 6, 2012
Regioselective synthesis of unsymmetrical C-aryl glycosides using silicon tethers as disposable linkers
David E Kaelin1, Steven M Sparks, Hilary R Plake
1Department of Chemistry and Biochemistry, University of Texas, Austin, TX 78712-0615, USA.
Abstract:
Silicon tethers were employed to control the regiochemistry of Diels-Alder reactions between substituted benzynes and glycosyl furans as a key step in the syntheses of unsymmetrical representatives of three major groups of C-aryl glycosides. The cycloaddition precursors were readily prepared by O-alkylation of substituted phenols with various sugar-substituted furylsilane derivatives. Selective deprotonation on the benzene ring of these ethers led to a benzyne that underwent an intramolecular Diels-Alder reaction to give bridged cycloadducts. Fluoride-induced removal of the silicon tether and acid-catalyzed ring opening of the oxabicycloheptadiene subunit yielded the desired C-aryl glycosides as single isomers.
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