Unusual C–C bond cleavage of an α-trifloxy Sialic acid hemiacetal under Lattrell-Dax conditions. (January 2022)

• Record Type: Journal Article
• Authors: Jana, Santanu; Crich, David
• Is Part Of: Carbohydrate research. Volume 511(2022)
• Publication Date: 2022-01
• Subjects: Sialic acid -- Oxidative cleavage -- Lattrell-Dax reaction -- Furanolactone -- Conformational analysis; Carbohydrates -- Periodicals; Chemistry, Organic -- Periodicals; Biochemistry -- Periodicals; Carbohydrates -- Periodicals; Chimie organique -- Périodiques; Glucides -- Périodiques; Biochemistry; Carbohydrates; Chemistry, Organic; Periodicals; Electronic journals; 507.78
• DOI: 10.1016/j.carres.2021.108494
• Languages: English
• ISSNs: 0008-6215

Abstract

Abstract: We describe the novel oxidative fragmentation of methyl (5-acetamido-4, 7, 8, 9-tetra- O -acetyl-5-deoxy-3- O -trifluoromethanesulfonyl-β-D- erythro -L- gluco -2-nonulopyranos)onate 2 on stirring with sodium nitrite in DMF to give the novel 3-acetamido-2, 5, 6, 7-tetra- O -acetyl-d - glycero -d -galacto-heptono-1, 4-lactone 3 in excellent yield. Stirring of the same triflate with sodium carbonate on the other hand affords the novel methyl (5-acetamido-7, 8, 9-tri- O -acetyl-3, 6-anhydro-5-deoxy-d -manno-3-ene-2-nonulos)onate 19 also in excellent yield. Reduction of the heptono lactone with sodium borohydride followed by acetylation gives a peracetylated aminodeoxyheptitol 6 that adopts the zig zag conformation of its carbon backbone. Graphical abstract: Image 1 Highlights: Oxidative cleavage and ring contraction of a nonulosonate ester triflate derivative. Base-mediated ring contraction and elimination of a nonulosonate ester triflate derivative. Synthesis and conformational analysis of novel heptitols