2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose | 151428-17-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose
• 英文别名: methyl 2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose；Methyl 2,3-O-Isopropylidene-5-keto-α-D-mannofuranoside；1-[(3aS,4S,6S,6aR)-4-methoxy-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-6-yl]-2-hydroxyethanone
• CAS: 151428-17-0
• 化学式: C₁₀H₁₆O₆
• 分子量: 232.233
• InChiKey: GYWGGNPLTPTVAA-XGEHTFHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  74.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose 在 palladium dihydroxide Dowex 50W-X₈ 、 氢气 、 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， -78.0~25.0 ℃ 、344.73 kPa 条件下， 反应 103.0h， 生成 1-脱氧甘露伊霉素
  参考文献：
  名称：

  Expeditious Synthesis of Aza sugars by the Double Reductive Amination of Dicarbonyl Sugars

  摘要：

  Polyhydroxylated pyrrolidines and piperidines were prepared by the double reductive amination of dicarbonyl, sugars with primary amines and NaCNBH3 in MeOH. Stereocontrol in these reactions depended on the nature of the amine and dicarbonyl sugar. For example, 5-keto-D-fructose (7) gave three pyrrolidine stereoisomers, with the N-alkylated 2,5-anhydro-2,5-imino-D-glucitol predominating. Under similar reaction conditions with benzhydrylamine, 5-keto-D-glucose (20) afforded a 96:4 mixture of piperidines favoring D-gluco 25A, whereas 5-keto-D-mannose (6) produced a 67:33 mixture enriched in D-manno isomer 40. This method allowed for the direct and relatively short synthesis of 1-deoxynojirimycin (DNJ, 1) and 1-deoxymannojirimycin (DMJ, 5) and N-alkylated derivatives thereof. Similar reactions with O-protected 5-keto-D-glucose derivatives 21 and 22 were less stereoselective and lower yielding.

  DOI：

  10.1021/jo00090a040
• 作为产物：
  描述：

  methyl 2,3-O-isopropylidene-α-D-mannofuranoside 在 溴 、 二正丁基氧化锡 作用下， 生成 2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose
  参考文献：
  名称：

  Expeditious Synthesis of Aza sugars by the Double Reductive Amination of Dicarbonyl Sugars

  摘要：

  Polyhydroxylated pyrrolidines and piperidines were prepared by the double reductive amination of dicarbonyl, sugars with primary amines and NaCNBH3 in MeOH. Stereocontrol in these reactions depended on the nature of the amine and dicarbonyl sugar. For example, 5-keto-D-fructose (7) gave three pyrrolidine stereoisomers, with the N-alkylated 2,5-anhydro-2,5-imino-D-glucitol predominating. Under similar reaction conditions with benzhydrylamine, 5-keto-D-glucose (20) afforded a 96:4 mixture of piperidines favoring D-gluco 25A, whereas 5-keto-D-mannose (6) produced a 67:33 mixture enriched in D-manno isomer 40. This method allowed for the direct and relatively short synthesis of 1-deoxynojirimycin (DNJ, 1) and 1-deoxymannojirimycin (DMJ, 5) and N-alkylated derivatives thereof. Similar reactions with O-protected 5-keto-D-glucose derivatives 21 and 22 were less stereoselective and lower yielding.

  DOI：

  10.1021/jo00090a040

文献信息

• Synthesis of 4-Carbamoyl-2-oxazolidinones C-4-Linked with a Saccharide Moiety via Bucherer-Bergs Reaction of Hexofuranos-5-uloses
  作者：Miroslav Koóš、Júlia Mičová、Bohumil Steiner、Vratislav Langer、Dalma Gyepesová

  DOI：10.1055/s-2002-34222

  日期：——

  Application of the Bucherer-Bergs reaction to 6-O-unprotected hexofuranos-5-uloses led to the formation of 4-carbamoyl-2-oxazolidinones C-4-linked with a carbohydrate moiety instead of expected carbohydrate-C-5-linked hydantoin (imidazolidin-2,4-dione) derivatives. Starting from hexofuranos-5-uloses having all hydroxyl groups suitably protected, only corresponding saccharide-linked hydandoins were obtained.

  对未受保护的 6-O- hexofuranos-5-uloses 应用 Bucherer-Bergs 反应，可生成与碳水化合物分子 C-4 连接的 4-氨基甲酰基-2-噁唑烷酮，而不是预期的与碳水化合物分子 C-5 连接的海因（咪唑烷-2,4-二酮）衍生物。从所有羟基都得到适当保护的六呋喃糖-5-酮开始，只得到了相应的糖连接海因。
• Synthesis and structure determination of some nonanomerically C–C-linked serine glycoconjugates structurally related to mannojirimycin
  作者：Júlia Mičová、Bohumil Steiner、Miroslav Koóš、Vratislav Langer、Dalma Gyepesová

  DOI：10.1016/j.carres.2004.06.020

  日期：2004.9

  The Bucherer-Bergs reaction of methyl 2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosid-5-ulose gave (4'S)-4'-carbamoyl-4'-[methyl (4R)-2,3-O-isopropylidene-beta-L-erythrofuranosid-4-C-yl]-oxazolidin-2'-one instead of expected hydantoins. A mixture of hydantoins-(5'R)-triphenylmethoxymethyl-5'-[methyl (4R)-2,3-O-isopropylidene-beta-L-erythrofuranosid-4-C-yl]-imidazolidin-2',4'-dione and (5'S)-triphenylmethoxymethyl-5'-[methyl (4R)-2,3-O-isopropylidene-beta-L-erythrofuranosid-4-C-yl]-imidazolidin-2',4'-dione was obtained from the 5-ulose having protected primary OH group at C-6. The 4'-S configuration of 2 as well as 5'S configuration of (5'S)-hydroxymethyl-5'-[methyl (4R)-2,3-O-isopropylidene-beta-L-erythrofuranosid-4-C-yl]-imidazolidin-2',4'-dione (9) was confirmed by X-ray crystallography. Corresponding a-amino acid methyl (5S)-5-amino-5-C-carboxy-5-deoxy-alpha-D-lyxo-hexofuranoside (alternative name: 2-[methyl (4R)-beta-L-erythrofuranosid-4-C-yl]-L-serine) (11) was obtained from the hydantoin 9 by acid hydrolysis of the isopropylidene and trityl groups followed by basic hydrolysis of the hydantoin ring. Analogous derivatives with 5-R configuration, formed in a minority, were also isolated and characterised. (C) 2004 Elsevier Ltd. All rights reserved.