Monday, 23 May 2005 - 3:50 PM
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This presentation is part of: Carbohydrates

Vinyl glycosides and carbohydrate vinyl ethers: Synthesis and applications

Robert Giuliano, Kevin Hughes, Christopher Cummings, and Tuan Nguyen. Villanova University, Villanova, PA

Vinyl glucopyranosides have been used as chiral  auxiliaries in cycloaddition  reactions, as precursors to branched glycals, as glycosyl donors, and in other applications. Vinyl glucopyranosides are most often synthesized by trans-vinylation reactions, by displacement reactions of glycosyl halides with bis(acylmethyl)mercury reagents, or by selenoxide or other elimination  reactions.  Recently, a mercury-free preparation of vinyl  ethers has been reported, in which the vinyl group is introduced by the elimination of mixed acetals with trimethylsilyl  trifluoromethanesulfonate in the presence of alkyl amines (Gassman method).1,2  We have applied this reaction to the synthesis of protected vinyl  a-D-glucopyranosides  as well as to related carbohydrate vinyl ethers.3   Hetero-Diels-Alder  reactions of the vinyl ethers have been carried out as part of an approach to disaccharides that contain highly deoxygentated  sugars.  These reactions are highly regioselective and give mainly endo cycloadducts. Cyclopropyl glycosides have also been prepared.                                             1.  Gassman, P.; Burns, S. J.; Pfister, K. B. J. Org.Chem.,1993, 58, 1449, 2. Dujardins, G.; Rossignol, S.; Brown, E. Tetrahderon.Lett., 1995, 36, 1653, 3. Edathil, J.; Nguyen, J.;  Hughes, K.; Boyko, W. J.; Giuliano, R. M. J. Carbohydr.Chem. 2001, 20, 81,

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