Highly Diastereoselective Synthesis of C‑Glycosides from Glycal Anomers

This Letter presents a highly diastereoselective synthesis of C-hydroxymethine glycosides from glycal anomers using a chiral N-heterocyclic carbene–copper catalyst. The high diastereoselectivity was synergistically controlled by the stereocenter of the substrate and chirality of the N-heterocyclic carbene–copper complex without being interrupted by the stereochemistry of C5 and the anomeric position. This approach enables the production of a diverse array of C-hydroxymethine glycosides using synthetically versatile glycals and various functionalized aldehydes.