On the Role of Neighboring Group Participation and Ortho Esters in β-Xylosylation: 13C NMR Observation of a Bridging 2-Phenyl-1,3-dioxalenium Ion

Publisher Website
Google Scholar
Abstract
The role of ortho esters in the formation of 2,3,4-tri-O-benzoyl-β-xylopyranosides from various donor/promoter pairs has been investigated. It is concluded that for the activation of sulfoxides with Tf2O, thioglycosides with PhSOTf, and bromides with AgOTf the anomeric configuration of the donor is of no consequence on the outcome of the reaction. In all methods studied, the presence or absence of a non-nucleophilic, hindered base is of crucial importance with ortho esters only being discernible in its presence. S-Phenyl 2,3,4-tri-O-benzoyl-1-deoxy-1-thia-β-d-xylopyranoside was synthesized enriched with 13C at each of the three carbonyl carbons. Activation of this thioglycoside with PhSOTf in CD2Cl2 at −78 °C with or without the base permits, for the first time, the observation by 13C NMR spectroscopy of a bridging dioxalenium ion as an intermediate in a neighboring group directed glycosylation. Quenching of this cation in the presence of the base leads to the ortho ester, whereas in the absence of the base the glycosides are the only products detected.