- Stereocontrolled Syntheses of Deoxyribonucleosides via Photoinduced Electron-Transfer Deoxygenation of Benzoyl-Protected Ribo- and Arabinonucleosides
-
The stereocontrolled, de novo syntheses of β-2′-deoxy-, α-2′-deoxy-, β-3′-deoxy-, and β-2′,3′-dideoxyribonucleosides are described. Strategically protected ribose, arabinose, and xylose glycosylation precursors were synthesized bearing C2-esters capable of directing Vorbrueggen glycosylation. The key step is the regioselective deoxygenation of the desired hydroxyl group as either the benzoyl- or 3-(trifluoromethyl)benzoyl derivative. This deoxygenation is accomplished via a photoinduced electron-transfer (PET) mechanism using carbazole derivatives as the photosensitizer. The syntheses of the desired deoxynucleoside generally proceed in three steps from a common, readily available precursor.
- Wang, Zhiwei,Prudhomme, Daniel R.,Buck, Jason R.,Park, Minnie,Rizzo, Carmelo J.
-
p. 5969 - 5985
(2007/10/03)
-
- Synthesis of phosphonate analogues of 2-deoxyribose-1-phosphate
-
Phosphonate derivatives of 2-deoxyribose have been synthesized for the first time, by Lewis acid-mediated reaction of glycosyl donors with diisopropylhydroxymetylphosphonate for compounds 2 or with triisopropyl phosphite for compounds 3. Although, the selectivity of the reaction was moderate, in both cases the α-glycosides were predominantly obtained.
- Rubira, María-José,Pérez-Pérez, María-Jesús,Balzarini, Jan,Camarasa, María-José
-
p. 177 - 179
(2007/10/03)
-
- Radical Rearrangement of 2-O-(Diphenylphosphoryl)glycosyl Bromides. A New Synthesis for 2-Deoxy Disaccharides and 2-Deoxy Ribonucleosides
-
2-Deoxy-1-O-diphenylphosphoryl glycosides react with nucleophiles under mild conditions giving access to 2-deoxy disaccharides and nucleosides.The intermediate 2-deoxy-1-O-diphenylphosphoryl compounds were generated in situ by a radical 2 -> 1 migration of the phosphate ester group.This is the first observation of a rearrangement of a phosphate ester in radicals.ESR experiments and quenching of the radical at C2 by tin hydride or tin deuteride were used to detect the intermediates and to prove their structure.
- Koch, Andreas,Lamberth, Clemens,Wetterich, Frank,Giese, Bernd
-
p. 1083 - 1089
(2007/10/02)
-