A concise synthesis of l-gulose and its C-6 derivatives. (1st November 2022)

• Record Type: Journal Article
• Authors: Teng, Kai-Ching; Tseng, Kuei-Yao; Tzeng, Zheng-Hao; Hung, Shang-Cheng
• Is Part Of: Bioorganic & medicinal chemistry. Volume 73(2022)
• Publication Date: 2022-11-01
• Subjects: l-hexose -- 6-deoxy-l-hexose -- l-gulose -- Alginate -- Carbohydrate chemistry; Bioorganic chemistry -- Periodicals; Pharmaceutical chemistry -- Periodicals; Biochemistry -- Periodicals; Chemistry, Clinical -- Periodicals; Chemistry, Organic -- Periodicals; Chimie bio-organique -- Périodiques; Chimie pharmaceutique -- Périodiques; 615.19
• DOI: 10.1016/j.bmc.2022.117029
• Languages: English
• ISSNs: 0968-0896

Abstract

Graphical abstract: Abstract: A convenient route for the preparation of l -gulose and its C-6 derivatives starting from commercially available 2, 3:5, 6-diisopropylidene-d -mannofuranose via C-5 epimerization as the key step was developed. 1- O -Benzylation followed by regioselective hydrolysis of the 5, 6-isopropylidene group furnished benzyl 2, 3-isopropylidene-α-d -mannofuranoside, which was subjected upon regioselective one-pot 6- O -benzoylation and 5- O -mesylation, providing the corresponding 5-OMs-6-OBz derivative in excellent selectivity. Treatment of this mesylate compound with potassium t -butoxide to remove the benzoyl group followed by intramolecular SN 2 inversion led to benzyl 5, 6-anhydro-2, 3-isopropylidene-β-l -gulofuranoside, which could undergo not only nucleophilic substitutions to open the epoxide ring to give various C-6 derivatives, but also acidic hydrolysis to yield 1, 6-anhydro-β-l -gulopyranose for further transformation into l -gulopyranosyl pentaacetate.