The Journal of organic chemistry 2017 10 06() doi 10.1021/acs.joc.7b02027
Hydroxybenzotriazole is routinely used in peptide chemistry for reducing racemization due to the increased reactivity. In this manuscript, very stable hydroxybenzotriazolyl glucosides were identified to undergo glycosidation. The reaction was hypothesized to go through the remote activation by the Tf2O at the N3-site of HOBt followed by the extrusion of the oxocarbenium ion that was attacked by the glycosyl acceptor. Further, equilibration of the zwitterionic benzotriazolyl species makes the leaving group non-competitive and generates the nucleofuge that has been reconverted to the glycosyl donor. The reaction is mild, high yielding, fast and suitable for donors containing both C2-ethers and C2-esters as well. The regenerative-donor glycosidation strategy is promising as it enables us to regenerate the glycosyl donor for further utilization. The utility of the methodology for the oligosaccharide synthesis was demonstrated by the successful synthesis of the branched pentamannan core of the HIV1-gp120 complex.