title: Control of phosphoryl migratory transesterifications allows regioselecive access to sugar phosphates.
abstract: Phosphate esters in polyhydroxylated systems are normally blighted by uncontrolled migration under a variety of reaction conditions. Cesium fluoride is demonstrated as a reagent to control migration of primary phosphates during transesterifications. This allows easy exchange of phosphoryl protecting groups enabling enhanced synthetic strategic flexibility and regioselective phosphate installation. Mechanistic analysis suggests that a fluoride-induced extended solvent sphere modulates steric bulk at phosphorus to favor the primary position.
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Mitul K
authors.initials: MK
authors.lastname: Patel
authors.forename: Benjamin G
authors.initials: BG
authors.lastname: Davis
mesh_terms: D002586:Cesium / Q000737:chemistry; D004951:Esterification; D005459:Fluorides / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism; D013403:Sugar Phosphates / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D013403:Sugar Phosphates; D002586:Cesium; D005459:Fluorides; C027754:cesium fluoride