Neoglycorandomization is a chemical approach that leverages the chemoselective reaction between an N,Odisubstituted alkoxyamine unit with a reducing sugar to yield a neoglycoside. An alternative to "diversify then glycosylate" is "glycosylate then diversify." The idea is to prepare a small collection of key glycosylated precursors that serve as feedstocks in library assembly. The feedstock compounds, containing reactive handles on the aglycone, can be subsequently elaborated at sites distal from the glycosyl domain. Through the careful choice of precursor-reaction pairs, it should be possible to assemble highly focused libraries through short, flexible and protecting group-free sequences. We refer to this method for the preparation of glycosylated small molecule libraries as post-glycosylation diversification, or PGD. Here we report a proof-of-concept PGD study using desosamine as the key sugar for library synthesis. New glycosides prepared by this method were then characterized for their potential activity as antibiotic and immunomodulatory lead compounds.