One-pot Dess-Martin periodinane-mediated oxidative deprotection and olefination of trimethylsilyl-protected pyranosides and pyranoses

The selective functionalization of carbohydrates provides a powerful method for introducing structural complexity, allowing access to unique drug scaffolds with distinctive pharmaceutical profiles. Herein, we describe an efficient and selective carbon-carbon bond forming reaction of a variety of common trimethylsilyl-protected pyranosides and pyranoses at C-6 using a one-pot Dess-Martin periodinane-mediated oxidation deprotection. This is followed by addition of stabilized and non-stabilized ylides to generate alkenoate carbohydrates and related analogs in good to moderate yields. We also report on the rapid deprotection of the remaining trimethylsilyl ether groups in near quantitative yields using an acidic resin-mediated ethanolysis. [Display omitted] •One-pot C-6 oxidative deprotection and olefination of trimethylsilyl-protected pyranosides and pyranoses.•Use of Dess-Martin periodinane avoids the use of toxic chromium-based reagents; minimizes solvent and purification steps.•Anomeric site remains available for subsequent functionalization.•Acidic resin-mediated ethanolysis provides parent carbohydrate in near quantitative yield.•Convenient approach for glycodiversification strategies.