Total Synthesis of DL-Glucose, 3-O-Methyl-DL-glucose, and 3-Deoxy-DL-ribo-hexopyranose from 1,6:3,4-Dianhydro-β-DL-allo-hexopyranose, a Product Obtained from Acrolein Dimer

Abstract

The reaction of butyllithium in ether with 1,6:2,3-dianhydro-4-deoxy-β-DL-ribo-hexopyranose (1), a substance obtained in five steps from acrolein dimer, gave 1,6-anhydro-3,4-dideoxy-β-DL-erythro-hex-3-enopyranose (2). The compound 1,6:3,4-dianhydro-β-DL-allo-hexopyranose (3), obtained from 2, was converted by reaction with aqueous barium hydroxide followed by hydrolysis of the product, to DL-glucose 5. Treatment of 3 with sodium methoxide in methanol followed by acid hydrolysis of the 1,6-anhydro intermediate 6, gave 3-O-methyl-DL-glucose (7). The same intermediate, 6, along with the methyl glycoside 8, could be obtained by the acid-catalyzed reaction of 3 with methanol. Lithium aluminum hydride reacted with 3 to form 1,6-anhydro-3-deoxy-β-DL-ribo-hexopyranose (9), which was hydrolyzed readily to 3-deoxy-DL-ribo-hexopyranose (10).Yields were excellent throughout. All products obtained from the oxirane 3 were those resulting only from trans diaxial opening of the oxirane ring.