Oxidation of 3-C-(2-amino-2-deoxy-D-glucopyranosyl)-1-propene compounds and the structure of 3-C-(2-amino-2-deoxy-D-glucopyranosyl)-1,2-propanediol derivatives for a synthesis of 2,3-didehydro-2,7-dideoxy-N-acetylneuraminic acid.
Oxidation of 5-acetamido-4,8-anhydro-1,2,3,5-tetradeoxy-D-glycero-D-ido-non-1-enitol [3-C-(2-amino-2-deoxy-beta-D-glucopyranosyl)-1-propene] was studied to search for preparative routes to aminodeoxy didehydro nonulosonic acid derivatives. Since only moderate chiral induction was observed with osmium tetroxide dihydroxylation as well as with peracid epoxidation, the catalytic asymmetric dihydroxylation conditions were applied to give the stereocontrolled formation of 1,2-propanediol derivatives. The structures of these diastereoisomeric 1,2-propanediol derivatives were determined by X-ray crystallographic analyses. The formation of diastereoisomeric 1,2-propanediols also varied with the nature of 2-substituent on the aminodoexy glycosyl moiety. Thus 5-acetamido-4,8-anhydro-3,5-dideoxy-D-erythro-L-ido-nonitol [(2S)-3-C-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-1,2-propanediol] was obtained predominantly up to 70% from 3-C-(2-acetamido-2-deoxyglycosyl)-1-propene by the use of ADmixbeta reagent. The (2S)-propanediol derivative was transformed in a five-step reaction sequence to 2,3-didehydro-2,7-dideoxy-N-acetylneuraminic acid.
Machinami
Tomoya
T
Department of Chemistry, College of Science and Technology, Meisei University, Hino, Tokyo 191-8506, Japan. machinam@chem.meisei-u.ac.jp
Itaba
Yasuyuki
Y
Kayama
Ayumi
A
Fujimoto
Takashi
T
Suami
Tetsuo
T
D000475:Alkenes / Q000737:chemistry; D018360:Crystallography, X-Ray; D006900:Hydroxylation; D015394:Molecular Structure; D019158:N-Acetylneuraminic Acid / Q000031:analogs & derivatives / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D011409:Propylene Glycols / Q000737:chemistry; D012794:Sialic Acids / Q000138:chemical synthesis*; D013237:Stereoisomerism
C475339:2,3-didehydro-2,7-dideoxy-N-acetylneuraminic acid.; D000475:Alkenes; D011409:Propylene Glycols; D012794:Sialic Acids; C013658:propylene; D019158:N-Acetylneuraminic Acid