•Strategy for regioselective sulfation of saccharides is developed.•Application of highly α-selective dehydrative glycosylation.•Demonstration of the utility of trichloroethylsulfate group as a means for the introduction of sulfate monoesters.Sulfated liposaccharides are known inhibitors of telomerase and here we describe the synthesis of a series of sulfated liposaccharides inspired by the natural product axinelloside A, reported to act as an inhibitor of human telomerase. We established a robust and scalable synthetic route to galactosyl liposaccharides capitalizing on a series of regioselective acylation reactions with 2-decenoic acid and imidazolium sulfate esters.Download high-res image (54KB)Download full-size image

Cyclic phosphonium anhydrides generated from bis-phosphine oxides and trifluoromethanesulfonic anhydride are shown as general coupling reagents in a dehydrative glycosylation reaction of C1-hemiacetals. This reaction protocol is characterized by a broad substrate scope and high yields, including reactions of O-, C-, N-, and S-based nucleophiles with furanose, pyranose, and deoxysugar donors.

We demonstrate that configurationally stable anomeric stannanes undergo a stereospecific cross-coupling reaction with aromatic halides in the presence of a palladium catalyst with exceptionally high levels of stereocontrol. In addition to a broad substrate scope (>40 examples), this reaction eliminates critical problems inherent to nucleophilic displacement methods and is applicable to (hetero)aromatics, peptides, pharmaceuticals, common monosaccharides, and saccharides containing free hydroxyl groups.

•scyllo-Inositol is a rare member of the inositol family and no asymmetric synthesis has been reported.•Starting from inexpensive d-glucose, stereoselective Ferrier-II carbocyclization afforded the myo-inositol core.•The configuration of the final product was then adjusted in a two-step conversion of myo-inositol to scyllo-inositol.scyllo-Inositol, a rare member of the inositol family, is present in axinelloside A, a marine metabolite with interesting inhibitory activity against human telomerase. Here, we present a concise synthesis of asymmetrically substituted scyllo-inositol starting from inexpensive d-glucose. Our synthetic approach capitalizes on Ferrier rearrangement of vinyl acetate and stereoselective reduction of the resultant ketone to establish the scyllo-inositol core. The protocol provides access to large quantities of scyllo-inositol in 10 steps from commercially available materials.

Cyclic phosphonium anhydrides generated from bis-phosphine oxides and trifluoromethanesulfonic anhydride are shown as general coupling reagents in a dehydrative glycosylation reaction of C1-hemiacetals. This reaction protocol is characterized by a broad substrate scope and high yields, including reactions of O-, C-, N-, and S-based nucleophiles with furanose, pyranose, and deoxysugar donors.