Stereoselective Syntheses of 3′-Hydroxyamino- and 3′-Methoxyamino-2′,3′-Dideoxynucleosides

Aminonucleosides are used as key motifs in medicinal and bioconjugate chemistry; however, existing strategies toward 3'-hypernucleophilic amine systems do not readily deliver deoxyribo -configured products. We report diastereoselective syntheses of deoxyribo - and deoxyxylo -configured 3'-hydroxyamino- and 3'-methoxyamino-nucelosides from 3'-imine intermediates. The presence or absence of the 5'-hydroxyl-group protection dictates facial selectivity via inter- or intramolecular delivery of hydride from BH 3 (borane). Protecting group screening gave one access to previously unknown 3'-methoxyamino-deoxyguanosine derivatives.