Oligo- and polysaccharides are highly relevant as renewable energy sources and materials, in nanotechnology and chemical biology due to their role as recognition motifs in biological systems. Effective synthetic access to a given saccharide is crucial to study structure-properties and structure-activity relationships. Syntheses of complex polysaccharides can be tedious, and often require a range of protecting group modifications before the desired glycosylation can occur. In addition, defining stereochemistry at the anomeric center is crucial for the shape and biological function of saccharides.
In order to extend the synthetic toolbox and develop effective, diastereoselective glycosylation methods, we envision an auxiliary-driven approach, wherein the auxiliary does not only spatially coordinate the reactants but at the same time act as the activator of donor (electrophile) and acceptor (nucleophile). Exploiting enthalpies of bond formation between different main group elements plays a crucial role in this approach and necessitates the synthesis of different auxilliaries.