Organic Letters 2013-01-18

Control of phosphoryl migratory transesterifications allows regioselecive access to sugar phosphates.

Mitul K Patel, Benjamin G Davis

Index: Org. Lett. 15(2) , 346-9, (2013)

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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.