title: Evidence of cation-coordination involvement in directing the regioselective di-inversion reaction of vicinal di-sulfonate esters.
abstract: Direct evidence has been obtained to confirm the unusual nucleophilic attack of an alkoxide at the S-center of sp(3)-hybridized sulfonyl esters. The unusual reaction pathway leads to S-O bond scission which is crucial for the regio- and stereoselective conversion of 2,3-di-O-sulfonates of 4,6-O-benzylidene-β-D-galactopyranosides into β-D-idopyranosides. In addition, strong evidence has been provided to clarify the role of the alkali counter-cation in the transformation. The cation is believed to influence the reaction rate via coordination to an oxygen in the sulfonate ester; the presence of a neighboring ring oxygen oriented in a cis-relationship greatly enhances reactivity of the sulfonyl ester.
authors: Alberta Glycomics Centre, Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada.
authors: Rachel
authors: R
authors: Hevey
authors: Chang-Chun
authors: CC
authors: Ling
mesh_terms: D002412:Cations / Q000737:chemistry; D004952:Esters / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D002412:Cations; D004952:Esters; D013451:Sulfonic Acids