甲基-alpha-D-昆布二糖苷七乙酸酯 | 7322-42-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 甲基-alpha-D-昆布二糖苷七乙酸酯
• 中文别名: 甲基-α-D-昆布二糖苷七乙酸酯
• 英文名称: methyl O-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-(1->3)-2,4,6-tri-O-acetyl-α-D-galactopyranoside
• 英文别名: methyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-glucopyranoside；2,4,6,2',3',4',6'-Hepta-O-acetyl-α-methyl-laminaribiosid；Methyl 2,4,6-tri-O-acetyl-3-O-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-alpha-D-glucopyranoside；[(2R,3R,4S,5R,6S)-3,5-diacetyloxy-6-methoxy-4-[(2S,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxyoxan-2-yl]methyl acetate
• CAS: 7322-42-1
• 化学式: C₂₇H₃₈O₁₈
• 分子量: 650.588
• InChiKey: UHSQXNOZAXQAJT-OTEFYFLSSA-N

物化性质

• 熔点：
  188-189°C
• 沸点：
  649.8±55.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  45
• 可旋转键数：
  19
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  221
• 氢给体数：
  0
• 氢受体数：
  18

反应信息

• 作为产物：
  描述：

  4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 、 copper(l) iodide 、 三氟甲磺酸 、 氨 、 sodium 、 四丁基碘化铵 、 N,N-二异丙基乙胺 、 sodium hydroxide 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 48.75h， 生成 甲基-alpha-D-昆布二糖苷七乙酸酯
  参考文献：
  名称：

  通过点击反应介导的间隔物生成随后间隔物裂解的分子内糖苷化

  摘要：

  具有连位羟基的 2-O-炔丙基取代的糖基供体和 O-(2-叠氮基苄基)-取代的受体容易进行点击反应。以 N-碘代琥珀酰亚胺/三氟甲磺酸为激活系统的分子内糖苷化得到 β-(1-3)- 和 α-(1-2)-连接的二糖，作为 14 元大环的一部分。提出了这些反应的描述，考虑供体和受体连接位点以及官能团的立体化学。对包含在间隔基中的 2-O-连接的 1-芳基-1,2,3-三唑-4-基甲基基团对异头异构选择性的影响的研究表明没有嵌合辅助。此外，还表明间隔基团在 Birch 还原条件下很容易裂解。

  DOI：

  10.1002/ejoc.201201076

文献信息

• Efficient Intramolecular Glycosylation Supported by a Rigid Spacer
  作者：Matthias Müller、Ursula Huchel、Armin Geyer、Richard R. Schmidt

  DOI：10.1021/jo990132e

  日期：1999.8.1

  The m-xylylene moiety was employed as rigid spacer in intramolecular glycoside bond formation. Fifteen-membered macrocycle formation starting from 6-O-linked donor and 6- and 4-O-linked acceptor (5a,b, 6b) led exclusively to beta(1-4)- and beta(1-6)-linked compounds 7 beta and 8 beta, respectively, which gave cellobioside and gentiobioside derivatives. The glycosylation yields could be improved by 14-membered macrocycle formation. In the four cases studied, the donor was 6-O-linked to the spacer. For the acceptor linkage to the spacer and the accepting hydroxy group, relative D-/L-threo- and D-/L-erythro-arrangements were chosen. Standard glycosylation conditions led in three cases (13, 14, 23) only to beta-linkage in high yield (16 beta, 17 beta, 25 beta). For the transformation of 24, having a D-erythro-arrangement in the acceptor moiety, the alpha-anomer 26 alpha was preferentially obtained. Limitation of the conformational space of the donor and the acceptor as in 31, which is stereochemically identical with 24, led to the corresponding alpha-glycoside 32 alpha in 87% yield. Synthesis of a pseudo mirror image of 23 [having 6-(D)/3-(D-threo)-arrangement], namely 35, having 3(L)/6-(L-threo)-arrangement of the donor and acceptor moieties, expectedly gave only alpha-glycoside 36 alpha in very high yield. Thus, the efficiency and versatility of this conceptual approach to intramolecular glycoside bond formation is exhibited.
• Temeriusz, Andrzej; Piekarska, Boguslawa; Radomski, Jan, Polish Journal of Chemistry, 1982, vol. 56, # 1, p. 141 - 147
  作者：Temeriusz, Andrzej、Piekarska, Boguslawa、Radomski, Jan、Stepinski, Janusz

  DOI：——

  日期：——
• Template directed cyclo-glycosylation: Effect of the anchoring sites of the spacer and temperature in the regio- and stereo-selectivity of the glycosylation
  作者：Serafín Valverde、Ana M. Gómez、J. Cristóbal López、Bernardo Herradón

  DOI：10.1016/0040-4039(95)02316-x

  日期：1996.2

  The anchoring sites of the spacer and the reaction temperature have a remarkable effect on the regio- and stereo-selectivity of intramolecular macrocyclic glycosylation reactions of several template linked monosaccharides leading to macrocyclic disaccharides and thence to disaccharides.
• Intramolecular Glycosidation by Click Reaction Mediated Spacer Generation Followed by Spacer Cleavage
  作者：Amit Kumar、Yiqun Geng、Richard R. Schmidt

  DOI：10.1002/ejoc.201201076

  日期：2012.12

  glycosidation with N-iodosuccinimide/trifluoromethansulfonic acid as the activating system afforded β-(1–3)- and α-(1–2)-linked disaccharides as part of 14-membered macrocycles. Descriptors for these reactions are proposed that consider the donor and acceptor attachment sites and the stereochemistry of the functional groups. Investigation of the influence of 2-O-linked 1-aryl-1,2,3-triazol-4-ylmethyl

  具有连位羟基的 2-O-炔丙基取代的糖基供体和 O-(2-叠氮基苄基)-取代的受体容易进行点击反应。以 N-碘代琥珀酰亚胺/三氟甲磺酸为激活系统的分子内糖苷化得到 β-(1-3)- 和 α-(1-2)-连接的二糖，作为 14 元大环的一部分。提出了这些反应的描述，考虑供体和受体连接位点以及官能团的立体化学。对包含在间隔基中的 2-O-连接的 1-芳基-1,2,3-三唑-4-基甲基基团对异头异构选择性的影响的研究表明没有嵌合辅助。此外，还表明间隔基团在 Birch 还原条件下很容易裂解。