Relative reactivity evaluations showed the graded arming of toluenyl thioglucosides by variously positioned silyl groups but not by their acyl counterparts. These findings were applied in reactivity-based one-pot assembly of linker-attached Lc4 and IV2Fuc-Lc4, which are components of human embryonic stem cell surface. The sugar鈥揼alectin-1 binding was also examined.