Various glycal 3-carbamates undergo rhodium(II)-catalyzed oxidative cyclization with incorporation of an alcohol nucleophile at the anomeric site. The overall process--amidoglycosylation--likely proceeds via a rhodium-complexed nitrene and provides 2-amino sugars having a 1,2-trans-2,3-cis stereoarray. Anomeric stereoselectivity and partitioning between amidoglycosylation and an undesired C3-H oxidation pathway depend on the relative stereochemistry within the starting glycal 3-carbamate and on the 4O and 6O protecting groups. Our studies have led us to a mechanistic paradigm for stereo- and chemoselectivity in these metallanitrene-mediated amidoglycosylations.