Synthesis of Glycosyl Azides by the Addition of Phenylselenenyl Azide to Glycals

Abstract
The addition of phenylselenenyl azide to glycals is carried out under conditions that give 2-deoxy-2-phenylselenoglycosyl azides. This regiochemistry is opposite to that obtained under free-radical conditions, which are known to produce 2-azido-2-deoxyselenoglycosides. The addition reaction is carried out with phenylselenenyl chloride and sodium azide in dimethylformamide, and is stereoselective for trans addition. Tri-O-benzyl-d-glucal and di-O-benzyl-l-rhamnal each gave two addition products, in which the phenylselenyl and azido groups were either trans diaxial or trans diequatorial. Tri-O-benzyl-d-galactal gave only the trans diaxial addition product.
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