Solid-phase synthesis of oligosaccharides and on-resin quantitative monitoring using gated decoupling 13C NMR

A general strategy for solid-phase oligosaccharide synthesis capable of nondestructive quantitative monitoring has been developed. The synthesis was carried out on TentaGel using thioglycosides as glycosylating agents and dimethylthiomethylsulfonium triflate as the activator. An acylsulfonamide linker was introduced to cleave the oligosaccharide from the resin. The solid-phase reactions were monitored quantitatively by using the inverse gated decoupling technique of C-13 NMR, where two C-13-enriched markers were used to monitor the reactions: one was 13C-enriched glycine incorporated as a part of the linker and as an internal standard, and the other was a 13C-enriched acetyl group used as a protecting group of the glycosylation reagent. A representative synthesis of sialyl Lewis X branched tetrasaccharide was demonstrated.