2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-glucopyranoside | 117253-03-9

• 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-glucopyranoside
• 英文别名: (4aR,6R,7R,8R,8aS)-2-phenyl-6-(2-trimethylsilylethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-7,8-diol
• CAS: 117253-03-9
• 化学式: C₁₈H₂₈O₆Si
• 分子量: 368.502
• InChiKey: VHVMJWGDZRGIAG-DBISQMLMSA-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-glucopyranoside 在 盐酸 、 氢氧化钾 、 3 A molecular sieve 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 15.0h， 生成 2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  2-(Trimethylsilyl)ethyl glycosides. 3. Synthesis, anomeric deblocking, and transformation into 1,2-trans 1-O-acyl sugars

  摘要：

  DOI：

  10.1021/jo00259a006
• 作为产物：
  描述：

  2-(trimethylsilyl)ethyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside 在 Amberlite IRA 910 、 对甲苯磺酸 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 5.0h， 生成 2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-glucopyranoside
  参考文献：
  名称：

  具有固定羧酸基团的Sialyl Lewis x模拟物的合成：阐明Sialyl Lewis x生物活性构象的化学方法。

  摘要：

  溶液和唾液酸化的路易斯x（sLe（x））的生物活性构象之间的关系已通过化学方法解决。为了模拟sLe（x）1的最佳溶液构象，设计并合成了更刚性的类似物2。1的唾液酸残基被固定在与半乳糖融合的六元环缩醛的赤道位置的羧酸官能团取代。由于熵的考虑，如果优选的溶液构象和sLe（x）的结合形式相似，则有望提高生物活性。由于在E-选择素结合测定中发现模拟物2是无活性的，因此sLe（x）的结合形式很可能与当时的溶液构象不同。

  DOI：

  10.1021/jo951067l

文献信息

• Synthetic Studies on Polysaccharide HS-142-1, a Novel Nonpeptide Antagonist for the Atrial Natriuretic Peptide Receptor: Syntheses of the Gentiobiosyl Fragments
  作者：Yi Qiu、Yoshiaki Nakahara、Tomoya Ogawa

  DOI：10.1271/bbb.60.986

  日期：1996.1

  Possible disaccharide fragments of the major component of HS-142-1, a novel polysaccharide antagonist for functional atrial natriuretic peptide (ANP) receptors, O-(4-O-caproyl-β-D-glucopyranosyl)-(l →6)-4-O- caproy- 1-D-glucopyranose (1) and O-(3-O-caproyl-β-D-glucopyranosyl)-(l→6)-3-O-caproyl-D-glucopyranose (2), were respectively synthesized in a stereo- and regio-controlled manner. Deprotection of 2, 2ʹ-di-O-caproyl derivative 35 gave a complex mixture due to undesired acyl migration. In contrast, 2, 4ʹ-di-O-caproyl analog 39 was successfully deprotected to give O-(4-O-caproyl-β-D-glucopyranosyI)-(l →6)-2-O-caproyl-D-gluco-pyranose (40).

  可能的二糖片段是HS-142-1的主要成分，这是一种新的多糖拮抗剂，用于功能性心房利钠肽（ANP）受体，分别是O-(4-O-己酰基-β-D-葡萄糖吡喃糖基)-(l →6)-4-O-己酰基-1-D-葡萄糖吡喃糖（1）和O-(3-O-己酰基-β-D-葡萄糖吡喃糖基)-(l→6)-3-O-己酰基-D-葡萄糖吡喃糖（2），以立体和区域控制的方式合成。去保护2, 2ʹ-二-O-己酸酯衍生物35时，由于不希望的酸酰迁移，产生了复杂的混合物。相比之下，2, 4ʹ-二-O-己酸酯类似物39成功去保护，给出了O-(4-O-己酰基-β-D-葡萄糖吡喃糖基)-(l →6)-2-O-己酰基-D-葡萄糖吡喃糖（40）。
• Design and Synthesis of Gentiohexaosyl Derivatives for an ANP Receptor Antagonist, HS-142–1
  作者：Yi Qiu、Yoshiaki Nakahara、Tomoya Ogawa

  DOI：10.1271/bbb.60.1308

  日期：1996.1

  A hexaosyl fragment of the major component of lipooligosaccharide HS-142–1, O-(3-O-caproyl-β-d-glucopyranosyl)-(1 → 6)-[O-(β-d-glucopyranosyl)-(1 → 6)-O-(3-O-caproyl-β-d-glucopyranosyl)-(1 → 6)]2-d-glucopyranose (1), was efficiently synthesized by block synthesis. More stable analogs, O-(3-O-hexyl-β-d-glucopyranosyl)-(1 → 6)-[O-(β-d-glucopyranosyl)-(1 → 6)-O-(3-O-hexyl-β-d-glucopyranosyl)-(1 → 6)]2-d-glucopyranose (4) and O-(3-O-caproyl-2,4,6-tri-O-methyl-β-d-glucopyranosyl)-(1→6)-[O-(2,3,4-tri-O-methyl-β-d-glucopyranosyl)-(1→6)-O-(3-O-caproyl-2,4-di-O-methyl-β-d-glucopyranosyl)-(1→6)]2–2,3,4-tri-O-methyl-d-glucopyranose (2), were also designed and synthesized in a similar manner.

  通过嵌段聚合法高效合成了脂寡糖 HS-142-1 主要成分 O-(3-O-己基-β-d-吡喃葡萄糖基)-(1 → 6)-[O-(β-d-吡喃葡萄糖基)-(1 → 6)-O-(3-O-己基-β-d-吡喃葡萄糖基)-(1 → 6)]2-d-吡喃葡萄糖（1）的己基片段。更稳定的类似物是 O-(3-O-己基-β-d-吡喃葡萄糖基)-(1 → 6)-[O-(β-d-吡喃葡萄糖基)-(1 → 6)-O-(3-O-己基-β-d-吡喃葡萄糖基)-(1 → 6)]2-d-吡喃葡萄糖（4）和 O-(3-O-己基-2、4,6-tri-O-methyl-β-d-glucopyranosyl)-(1→6)-[O-(2,(1→6)-O-(3-O-己酰基-2,4-二-O-甲基-β-d-吡喃葡萄糖基)-(1→6)]2-2,3,4-三-O-甲基-d-吡喃葡萄糖 (2)，也是以类似的方法设计和合成的。
• Ellagitannin Chemistry. The First Total Chemical Synthesis of an O(2),O(3)-Galloyl-Coupled Ellagitannin, Sanguiin H-5
  作者：Ken S. Feldman、Aruna Sambandam

  DOI：10.1021/jo00130a016

  日期：1995.12

  The biomimetic synthesis of sanguiin H-5 (1) was accomplished through the diastereoselective formation of the crucial biphenyl carbon-carbon bond between galloyl moieties at the O(2) and O(3) positions of an appropriately protected glucose-derived precursor. Furthermore, the beta-anomeric galloyl linkage was established with complete stereochemical control.
• Synthesis of sialyl Lex ganglioside analogues sulfated at C-6 of either the galactose or N-acetylglucosamine residues, and at both of the galactose and N-acetylglucosamine residues: probes for clarifying the real carbohydrate ligand of L-selectin
  作者：Shiro Komba、Hideharu Ishida、Makoto Kiso、Akira Hasegawa

  DOI：10.1016/s0008-6215(96)90188-3

  日期：1996.5
• Synthesis of the 3′-C-carboxymethyl Lewis X derivative: a novel selectin blocker
  作者：Hideharu Ishida、Hiroyuki Hosokawa、Hirosato Kondo、Makoto Kiso、Akira Hasegawa

  DOI：10.1016/s0008-6215(97)00156-0

  日期：1997.9

  The 3'-C-carboxymethyl Le(x) derivative carrying the 2-(tetradecyl)hexadecyl residue was synthesized by employing 3'-C-carboxymethyl galactose as a key intermediate, which was prepared from the suitably protected galactose by Swern oxidation and Wittig-Horner carboxymethylenation, followed by stereoselective reduction of the double bond. The compound obtained showed much more potent activity as a selectin blocker than the sialyl Lex derivative with 2-(tetradecyl)hexadecyl residue. (C) 1997 Elsevier Science Ltd.