Stereoselective Glycosylation for 1,2-<i>cis</i>-Aminoglycoside Assembly by Cooperative Atom Transfer Catalysis

We report here a new catalytic method for exclusively 1,2-<i>cis</i>-α-selective glycosylation that assembles a wide variety of 1,2-<i>cis</i>-aminoglycosidic linkages in complex glycans and glycoconjugates. Mechanistic studies revealed a unique glycosylation mechanism in which the iron catalyst activates a glycosyl acceptor and an oxidant when it facilitates the cooperative atom transfer of both moieties to a glycosyl donor in an exclusively <i>cis</i>-selective manner. This catalytic approach is effective for a broad range of glycosyl donors and acceptors, and it can be operated in a reiterative fashion and scaled up to the multigram scale.