2,3,4,6-tetra-O-benzyl-1-C-vinyl-α-D-galactopyranose | 352020-76-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,4,6-tetra-O-benzyl-1-C-vinyl-α-D-galactopyranose
• 英文别名: (2S,3R,4S,5S,6R)-2-ethenyl-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ol
• CAS: 352020-76-9
• 化学式: C₃₆H₃₈O₆
• 分子量: 566.694
• InChiKey: FGULDCLPYKKIBB-BVMCXEQJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  42
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzyl-1-C-vinyl-α-D-galactopyranose 在 platinum on activated charcoal 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 sodium hydroxide 、 正丁基锂 、 sodium azide 、 三氟化硼乙醚 、 硫化氢 、 氢气 、 L-Selectride 、 potassium carbonate 、 三苯基膦 、 lithium diisopropyl amide 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醚 、 正己烷 、 正庚烷 、 二氯甲烷 、 乙基苯 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 59.33h， 生成 (3'S,4'R)-3'-amino-(E)-nonadec-5'-en-4'-olyl 2,3,4-tetra-O-benzyl-β-C-D-galactopyranoside
  参考文献：
  名称：

  Stereoselective Synthesis and Immunogenic Activity of the C-Analogue of Sulfatide

  摘要：

  The C-sulfatide 1b was synthesized through a [2,3]-Wittig sigmatropic rearrangement and a Horner-Wadsworth-Emmons olefination as the key steps. The C-analogue 1b is less immunogenic than natural sulfatide 1a, but induces a preferential secretion of the proinflammatory cytokine IFN-gamma.

  DOI：

  10.1021/ol061100y
• 作为产物：
  描述：

  乙烯基溴化镁 、 2,3,4,6-四-O-(苯基甲基)-D-半乳糖酸 D-内酯 以 四氢呋喃 为溶剂， 反应 1.0h， 以83.2%的产率得到2,3,4,6-tetra-O-benzyl-1-C-vinyl-α-D-galactopyranose
  参考文献：
  名称：

  A facile synthesis of 1′-C-alkyl-α-disaccharides from 1-C-alkyl-hexopyranoses and methyl 1-C-methyl-hexopyranosides

  摘要：

  Direct O-glycosidations using the 1-C-alkyl-2,3,4,6-tetra-O-benzyl-hexopyranoses as the glycosyl donors were carried out with a catalytic amount (0.2 equiv.) of trimethylsilyl trifluoromethanesulfonate (TMSOTf). The glycosidations proceeded alpha -stereoselectively and furnished the corresponding 1'-C-alkyl-alpha -disaccharides in 71-90% yields. The O-transglycosidations from the benzylated and acetylated methyl I-C-methyl-or-hexopyranosides to the corresponding 1'-C-methyl-alpha -O-disaccharides were also examined, respectively. These transglycosidations took place on alpha -stereoselectivity and provided the 1'-C-methyl-alpha -O-disaccharides as the sole products, implying that no neighboring group participation occured in the reactions. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00321-0

文献信息

• Synthetic Approach to <i>exo</i>-Glycals from 1-<i>C</i>-Vinyl-<scp>d</scp>-glycopyranose Derivatives via an S_N1′-Substitution Mechanism
  作者：Takashi Yamanoi、Yukari Nara、Sho Matsuda、Yoshiki Oda、Akihiro Yoshida、Kaname Katsuraya、Mikio Watanabe

  DOI：10.1055/s-2007-970751

  日期：2007.3

  describes a novel synthetic approach to exo- glycals from 1-C-vinyl-D-glycopyranose derivatives via the SN1¢- type substitution mechanism. The reaction of the 2,3,4,6-tetra-O- benzyl-1-C-vinyl-a-D-glycopyranose derivatives with several tri- methylsilylated nucleophiles was investigated. The reactions in dichloromethane-acetonitrile (1:1) at -78 °C in the presence of 20 mol% trimethylsilyl trifluoromethanesulfonate

  本文描述了一种通过 SN1 型取代机制从 1-C-乙烯基-D-吡喃葡萄糖衍生物合成外切糖的新方法。研究了 2,3,4,6-四-O-苄基-1-C-乙烯基-aD-吡喃葡萄糖衍生物与几种三甲基甲硅烷基化亲核试剂的反应。使用烯丙基三甲基硅烷和甲硅烷基烯醇醚作为亲核试剂，在 -78 °C 的二氯甲烷-乙腈 (1:1) 中，在 20 mol% 三氟甲磺酸三甲基甲硅烷基酯的存在下进行反应，立体选择性地以良好的收率提供了 Z-外-糖基衍生物。
• Stereoselective glycosylation of exo-glycals by microwave-assisted Ferrier rearrangement
  作者：Hui-Chang Lin、Chih-Chun Chang、Jia-Yi Chen、Chun-Hung Lin

  DOI：10.1016/j.tetasy.2004.11.044

  日期：2005.1

  exo-Glycosyl carbonates were shown to be efficient glycosyl donors in microwave-assisted glycosylation. In these reactions alpha-glycosyl additions occurred with excellent stereoselectivity and were complete in 4-8 min with 75-92% yield. Interestingly exo-glycals were found to have higher activity than endo-glycals and common glycosides, the reactions of which can be improved by the addition of Lewis acid to result in a higher yield and enhanced stereo selectivity. (C) 2004 Elsevier Ltd. All rights reserved.
• Reinvestigation of the Synthesis of Per-benzylated Glycosylethenes:  A New Result
  作者：Juan Xie、François Durrat、Jean-Marc Valéry

  DOI：10.1021/jo034795e

  日期：2003.10.1

  Addition of vinylmagnesium bromide on the perbenzylated glucono-1,5-lactone gave, after reduction with Et3SiH/BF3.Et2O, a mixture of the desired beta-C-vinyl glucoside 1 and the unexpected beta-C-but-3-enyl glucoside 3 resulting from double addition of vinylmagnesium bromide on the lactone. Similar results have been obtained with the perbenzylated galactono-1,5-lactone. This side reaction was then been explored to prepare beta-C-but-3-enyl glycosides and other beta-C-glycosyl derivatives by employing different Grignard reagents. An alternative approach to the per-benzylated glycosylethenes has been studied and compared.
• A facile synthesis of 1′-C-alkyl-α-disaccharides from 1-C-alkyl-hexopyranoses and methyl 1-C-methyl-hexopyranosides
  作者：Xiaoliu Li、Hiro Ohtake、Hideyo Takahashi、Shiro Ikegami

  DOI：10.1016/s0040-4020(01)00321-0

  日期：2001.5

  Direct O-glycosidations using the 1-C-alkyl-2,3,4,6-tetra-O-benzyl-hexopyranoses as the glycosyl donors were carried out with a catalytic amount (0.2 equiv.) of trimethylsilyl trifluoromethanesulfonate (TMSOTf). The glycosidations proceeded alpha -stereoselectively and furnished the corresponding 1'-C-alkyl-alpha -disaccharides in 71-90% yields. The O-transglycosidations from the benzylated and acetylated methyl I-C-methyl-or-hexopyranosides to the corresponding 1'-C-methyl-alpha -O-disaccharides were also examined, respectively. These transglycosidations took place on alpha -stereoselectivity and provided the 1'-C-methyl-alpha -O-disaccharides as the sole products, implying that no neighboring group participation occured in the reactions. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Stereoselective Synthesis and Immunogenic Activity of the <i>C</i>-Analogue of Sulfatide
  作者：Emilia Modica、Federica Compostella、Diego Colombo、Laura Franchini、Marco Cavallari、Lucia Mori、Gennaro De Libero、Luigi Panza、Fiamma Ronchetti

  DOI：10.1021/ol061100y

  日期：2006.7.1

  The C-sulfatide 1b was synthesized through a [2,3]-Wittig sigmatropic rearrangement and a Horner-Wadsworth-Emmons olefination as the key steps. The C-analogue 1b is less immunogenic than natural sulfatide 1a, but induces a preferential secretion of the proinflammatory cytokine IFN-gamma.