A concise synthesis of 4-nitrophenyl 2-azido-2-deoxy- and 2-acetamido-2-deoxy- d-mannopyranosides

• Published in: Carbohydrate research Vol. 340; no. 1; pp. 161 - 166
• Main Authors: Popelová, Alena, Kefurt, Karel, Hlaváčková, Martina, Moravcová, Jitka
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 17.01.2005; Elsevier
• Subjects: 2-Acetamido-2-deoxymannopyranoside; 2-Azido-2-deoxymannoside; 4-Nitrophenyl glycoside; Biochemistry & Molecular Biology; Chemistry; Chemistry, Applied; Chemistry, Organic; Life Sciences & Biomedicine; Magnetic Resonance Spectroscopy; Mannose - analogs & derivatives; Mannose - chemical synthesis; Mannose - chemistry; Migration of acetyl group; Molecular Structure; Physical Sciences; Science & Technology; 2-Acetamido-2-deoxymannopyranoside; 4-Nitrophenyl glycoside; 2-Azido-2-deoxymannoside; Migration of acetyl group; 2-acetamido-2-deoxymannopyranoside; 2-ACETAMIDO-2-DEOXY-BETA-D-MANNOPYRANOSIDE; AZIDES; 2-azido-2-deoxymannoside; MANNAC; 4-nitrophenyl glycoside; LIPOPOLYSACCHARIDE; D-MANNOSE; DISACCHARIDE; migration of acetyl group; DERIVATIVES; BINDING; ANTIGEN; POLYSACCHARIDE
• ISSN: 0008-6215; 1873-426X
• DOI: 10.1016/j.carres.2004.11.002

[Display omitted] 4-Nitrophenyl 3,4,6-tri- O-acetyl-2-azido-2-deoxy-α- and β- d-mannopyranosides were prepared from methyl 4,6- O-benzylidene-α- d-glucopyranoside and 1,3,4,6-tetra- O-acetyl-α- d-glucopyranose, respectively. Chemoselective reduction of both azides with hydrogen sulfide readily afforded 4-nitrophenyl 2-acetamido-4,6-di- O-acetyl-2-deoxy-α- d- and -β- d-mannopyranosides in higher yields than reduction with triphenylphosphine or a polymer-supported triarylphosphine. Subsequent de- O-acetylation yielded 4-nitrophenyl 2-acetamido-2-deoxy-α- d-mannopyranoside and 4-nitrophenyl 2-acetamido-2-deoxy-β- d-mannopyranoside in 20% and 44% overall yields, respectively.