Machinami Tomoya, Itaba Yasuyuki, Kayama Ayumi, Fujimoto Takashi, Suami Tetsuo
Department of Chemistry, College of Science and Technology, Meisei University, Hino, Tokyo 191-8506, Japan.
Carbohydr Res. 2002 Nov 19;337(21-23):1917-27. doi: 10.1016/s0008-6215(02)00225-2.
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.
对5-乙酰氨基-4,8-脱水-1,2,3,5-四脱氧-D-甘油-D-艾杜-壬-1-烯醇[3-C-(2-氨基-2-脱氧-β-D-吡喃葡萄糖基)-1-丙烯]的氧化反应进行了研究，以探寻氨基脱氧双脱氢壬糖醛酸衍生物的制备途径。由于四氧化锇二羟基化以及过氧酸环氧化反应仅观察到适度的手性诱导，因此采用催化不对称二羟基化条件来立体控制形成1,2-丙二醇衍生物。通过X射线晶体学分析确定了这些非对映异构的1,2-丙二醇衍生物的结构。非对映异构的1,2-丙二醇的形成也因氨基脱氧糖基部分上2-取代基的性质而异。因此，使用ADmixβ试剂，从3-C-(2-乙酰氨基-2-脱氧糖基)-1-丙烯中主要获得了高达70%的5-乙酰氨基-4,8-脱水-3,5-二脱氧-D-赤藓糖-L-艾杜糖醇[(2S)-3-C-(2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基)-1,2-丙二醇]。(2S)-丙二醇衍生物通过五步反应序列转化为2,3-双脱氢-2,7-二脱氧-N-乙酰神经氨酸。
