Modular and Stereoselective One-Pot Total Synthesis of Icosasaccharide Motif from Cordyceps sinensis EPS-1A Glycan.

The first stereoselective one-pot synthesis of the icosasaccharide motif of EPS-1A glycan from Cordyceps sinensis has been achieved. The synthetic approach highlights the following features: (1) merging reagent modulation and remote anchimeric assistance α-glycosylation strategy for the highly stereoselective formation of five and ten continuous 1,2-cis glucosidic bonds; (2) the strategic employment of glycosyl N-phenyltrifluoroacetimidates and glycosyl o-(1-phenylvinyl)benzoates as the matched pair for efficient orthogonal one-pot synthesis; and (3) [11 + 8 + 1] orthogonal one-pot glycosylation for the efficient assembly of the target icosasaccharide.

Insights into the Activation of Alkyne-Installed Glycosyl Donors with Dual Acidic Metal Catalysts: Reaction Pathway, Influencing Factors, and Enlightenment for Glycosylation.

The activation of alkyne-installed glycosyl donors with dual acidic metal catalysts were studied. Lewis and/or π acidity-activated pathways were observed for alkynyl carbonate-, ester-, and ether-type donors, and π acidity-promoted reaction mode afforded higher efficiency and yields. The activation mode for a certain metal catalyst is determined by the nature of catalysts itself, protecting groups on sugar rings, type of sugars, and structure of aglycones. The discovery gives us valuable insights into the glycosylation of alkyne-containing donors.

The total synthesis of rhynchosporosides via orthogonal one-pot glycosylation and stereoselective α-glycosylation strategies.

The efficient and collective synthesis of rhynchosporosides causing scald diseases has been achieved, which features orthogonal one-pot glycosylation on the basis of PTFAI glycosylation, Yu glycosylation, and PVB glycosylation and merging reagent modulation and remote anchimeric assistance (RMRAA) α-glucosylation strategies. The issues inherent to the thioglycoside-based orthogonal one-pot glycosylation strategy, such as aglycone transfer, have been precluded by this orthogonal one-pot glycosylation strategy, which can streamline glycan chemical synthesis.