Abstract
This account highlights an iron porphyrin-catalyzed highly stereospecific glycosylation method for glycal epoxides. This method is effective for a wide variety of previously challenging, hindered secondary sugar acceptors and a broad array of both electron-rich and electron-deficient glycal epoxide donors. It plays a pivot role in stereoselective heparan sulfate oligosaccharide synthesis, and the kinetic studies revealed that this glycosylation proceeds through SN2-type pathways with both primary and hindered secondary acceptors.