In summary, a method has been developed where an N-Troc protecting group was employed to enable the glycosylation reactions of glucosamine or galactosamine glycosyl fluoride donors and silyl protected acceptors under boron-catalyzed conditions to construct 1,2-trans aminosugar-containing glycosides. The reaction setup is operationally simple and rapid with commercially available B(C6F5)3 catalyst. This method can be conducted at room temperature without the requirement of rigid anhydrous conditions. One-pot iterative glycosylation can be performed to obtain complex glycosides, such as the precursors of mucin core glycans and human milk oligosaccharides, by installing different silyl protecting groups to aid differentiation of reactive sites on the acceptors. The above features place this approach as another powerful strategy that can be employed in synthetic glycan assembly approaches for building complex oligosaccharides that contain 2-amino-2-deoxy sugars in a catalytic, stereocontrolled, and convergent manner. orcid.org/0000-0002-4280-5996; E-mail: ysxu@umich.edu