Stereocontrolled Syntheses of Deoxyribonucleosides via Photoinduced Electron-Transfer Deoxygenation of Benzoyl-Protected Ribo- and Arabinonucleosides

• Published in: Journal of organic chemistry Vol. 65; no. 19; pp. 5969 - 5985
• Main Authors: Wang, Zhiwei, Prudhomme, Daniel R, Buck, Jason R, Park, Minnie, Rizzo, Carmelo J
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 22.09.2000; Amer Chemical Soc
• Subjects: Arabinonucleosides - chemistry; Chemistry; Chemistry, Organic; Deoxyribonucleosides - chemical synthesis; Physical Sciences; Ribonucleosides - chemistry; Science & Technology; Stereoisomerism; SECONDARY ALCOHOLS; ACID RELATED-COMPOUNDS; BASES; NUCLEOSIDE ANALOGS; RIBONUCLEOSIDES; ANTISENSE OLIGONUCLEOTIDES; DERIVATIVES; GENERAL PROCEDURE; HYBRIDIZATION PROPERTIES; NUCLEIC-ACIDS
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0003652

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 Vorbrüggen 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.