2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-galactopyranoside | 117252-96-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: 2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-galactopyranoside
• 英文别名: (4aR,6R,7R,8R,8aR)-2-phenyl-6-(2-trimethylsilylethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-7,8-diol
• CAS: 117252-96-7
• 化学式: C₁₈H₂₈O₆Si
• 分子量: 368.502
• InChiKey: VHVMJWGDZRGIAG-YJJCSNFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-galactopyranoside 在 palladium on activated charcoal 吡啶 、 N-碘代丁二酰亚胺 、 molecular sieve 、 三氟甲磺酸 、 3 A molecular sieve 、 4 A molecular sieve 、 三氟化硼乙醚 、 氢气 、 hydrochloric acid diethyl ether 、 sodium cyanoborohydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 溶剂黄146 、 乙腈 为溶剂， -45.0~25.0 ℃ 、101.33 kPa 条件下， 反应 9.63h， 生成 2-bromoethyl 2,3-di-O-acetyl-6,2'-O-methylidene-4-O-(3,4,6-tri-O-acetyl-α-D-galactropyranosyl)-β-D-galactopyranoside
  参考文献：
  名称：

  Restriction of Conformation in Galabiosides Via an O⁶−O²‘-Methylene Bridge

  摘要：

  Treatment of 2-(trimethylsilyl)ethyl 2,3-di-O-acetyl-4-O-(3,4,6-tri-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside (12) and 2-(trimethylsilyl)ethyl 2,3-di-O-benzyl-beta-D-glucopyranoside (15) with the novel reagent combination formaldehyde diphenylmercaptal-N-iodosuccinimide-trifluoromethanesulfonic acid [(PhS)(2)CH2/NIS/TfOH], gave the corresponding 6,2'-O- and 4,6-O-methylidene acetals 13 and 16 in 52% and 53% yield, respectively. Deacetylation of 13 gave 2-(trimethylsilyl)ethyl 4-O-alpha-D-galactopyranosyl-beta-D-galactopyranoside (1). The conformation of 1 was similar to that of the non-acetalated parent glycoside.

  DOI：

  10.1021/jo962371x
• 作为产物：
  描述：

  2-(trimethylsilyl)ethyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside 在 camphor-10-sulfonic acid 、 sodium methylate 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 23.0h， 生成 2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-galactopyranoside
  参考文献：
  名称：

  α-葡萄糖苷酶抑制剂阿卡波糖的生物合成研究：dTDP-4-氨基-4,6-二脱氧-α-D-葡萄糖的化学合成。

  摘要：

  为了研究假四糖阿卡波糖的生物合成，由半乳糖分16步制备了dTDP-4-氨基-4,6-二脱氧-α-D-葡萄糖（3）。在最初的保护基操纵之后，通过甲苯磺酸酯的氢化物置换使半乳糖的6-位脱氧。类似地，在与叠氮化钠反应时，在4-位的甲苯磺酰基被置换。通过使糖基三氯乙酰亚胺酸酯与磷酸二苄基酯反应，将所得的糖苷转化为糖基磷酸酯。随后除去苄基保护基并通过氢化和与活化的核苷磷酸偶合来还原叠氮化物，得​​到dTDP-4-氨基-4,6-二脱氧-α-D-葡萄糖。

  DOI：

  10.1016/s0008-6215(01)00323-8

文献信息

• Synthesis of 2-(Trimethylsilyl)ethyl 4-C-methyl-β-d-gluco-pyranuronamide. a derivative suitable as building block in synthesis of phosphoglycolipid antibiotics
  作者：Thomas G. Hansson、Niklas A. Plobeck

  DOI：10.1016/0040-4020(95)00693-3

  日期：1995.10

  The title compound, a protected derivative of a unique component in the moenuronamide group of phosphoglycolipid antibiotics has been synthesised in eleven steps and 30 % total yield from 2(trimethylsilyl) ethyl-β-d-galactopyranoside (6). The key step was a stereroselective addition of methylmagnesium chloride to ketone 11 to form the 4-C-methyl-glucopyranoside 12.

  标题化合物是磷酸糖脂类抗生素的单磺酰胺类中独特组分的受保护衍生物，已通过11个步骤合成，并且从2（三甲基甲硅烷基）乙基-β-d-吡喃半乳糖苷中获得30％的总收率（6）。关键步骤是将甲基氯化镁立体选择性地添加到酮11中，以形成4-C-甲基-吡喃葡萄糖苷12。
• Sulfuric acid immobilized on silica: an efficient promoter for one-pot acetalation–acetylation of sugar derivatives
  作者：Balaram Mukhopadhyay

  DOI：10.1016/j.tetlet.2006.04.118

  日期：2006.6

  Sulfuric acid immobilized on silica gel has been used as an efficient and safe alternative promoter for acetalation and subsequent acetylation of sugar glycosides using stoichiometric reagents without work-up. The synthesis of different types of per-O-acetylated acetals/ketals has been achieved from various types of O- and S-glycosides in excellent yields.

  固定在硅胶上的硫酸已被用作一种高效，安全的替代促进剂，用于使用化学计量试剂进行糖苷的缩醛化和随后的乙酰化，而无需进行后处理。已经从各种类型的O-和S-糖苷以优异的产率实现了不同类型的过-O-乙酰化缩醛/缩酮的合成。
• Synthesis of the globotetraose tetrasaccharide and terminal tri- and di-saccharide fragments
  作者：Ulf Nilsson、Asim K. Ray、Göran Magnusson

  DOI：10.1016/0008-6215(94)90010-8

  日期：1994.1

  groups. Removal of the anomeric TMSEt group of the globotetraoside and of the terminal trisaccharide, using trifluoroacetic acid-dichloromethane, gave the corresponding hemiacetal sugars 8 and 3. The TMSEt glycoside of the terminal trisaccharide was converted, via the 1-acetate, into the corresponding isobutyl (4) and 3-butylsulfonyl-2-[(butylsulfonyl)methyl]propyl (5) glycosides and into the TMSEt thioglycoside

  球四糖[β-D-GalNAc-（1-> 3）-alpha-D-Gal-（1-> 4）-beta-D-Gal-的2-（三甲基甲硅烷基）乙基（TMSEt）β-糖苷（1-> 4）-D-Glc]和末端三糖，以及末端二糖的甲基α-糖苷1，是由三氟甲磺酸银促进适当保护的半乳糖苷，galabioside和globotrioside的β-糖基化合成的醇与3,4,6-三-O-乙酰基-2-脱氧-2-邻苯二甲酰亚胺基-β-D-吡喃半乳糖苷氯，然后除去保护基。用三氟乙酸-二氯甲烷除去三糖四糖苷和末端三糖的异头TMSEt基团，得到相应的半缩醛糖8和3。末端三糖的TMSEt糖苷通过1-乙酸盐转化，
• Synthesis of Sialyl-α-(2→3)-Neolactotetraose Derivatives Containing Different Sialic Acids: Molecular Probes for Elucidation of Substrate Specificity of Human α1,3-Fucosyltransferases
  作者：Eiji Tanahashi、Kyoko Fukunaga、Yuko Ozawa、Tsuyoshi Toyoda、Hidcharu Ishida、Makoto Kiso

  DOI：10.1080/07328300008544114

  日期：2000.1

  A series of sialyl-alpha-(2-->3)-neolactotetraose derivatives containing N-acetyl-(NeuAc), N-glycolyl- (NeuGc) and N-butanoylneuraminic acid, and 3-deoxy-D-glycero-D-galacto-2-nonulosonic acid (KDN) have systematically been synthesized as molecular probes for elucidation of substrate specificity of human alpha 1,3-fucosyltransferases (Fuc-TVII and Fuc-TVI). 2-Methyl-(3,4, 6-tri-O-acetyl-1,2-dideoxy-alpha-D-glucopylano)-[2',1' :4,5]-2-oxazoline (1) was coupled with 2-(trimethyl-silyl)-ethyl (2,4,6-tri-O-benzyl-beta-D-galactopyranosyl) -(1 --> 4)-2,3,6-tri-O-benzyl-beta-D-glucopyranoside (2) to give a trisaccharide 3 which, upon successive O-deacetylation, benzylidenation and reductive opening of the benzylidene group, afforded a common glycosyl acceptor 5. Glycosylation of 5 with sialyl-alpha-(2-->3)-galactose donors 6-8, 19 and 21 gave the corresponding pentasaccharides 22-25, which were converted to a series of sialyl-alpha-(2-->3)-neolactotetraose derivatives 30-33. In the competitive enzyme assay, the NeuGc derivative 32 showed the most potent activity for Fuc-TVII, while the KDN derivative 31 was less active than the standard NeuAc derivative 30. In contrast, the N-butanoylation of neuraminic acid enhanced the activity for Fuc-TVI.
• 2-(Trimethylsilyl)ethyl glycosides. 3. Synthesis, anomeric deblocking, and transformation into 1,2-trans 1-O-acyl sugars
  作者：Karl Jansson、Stefan Ahlfors、Torbjoern Frejd、Jan Kihlberg、Goeran Magnusson、Jan Dahmen、Ghazi Noori、Kristina Stenvall

  DOI：10.1021/jo00259a006

  日期：1988.11