methyl (2,3,4,6-tetra-O-(4-chlorobenzyl)-β-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (2,3,4,6-tetra-O-(4-chlorobenzyl)-β-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: methyl 2,3,4-tri-O-benzyl-6-O-(2,3,4,6-tetra-O-(p-chlorobenzyl)-β-D-glucopyranosyl)-α-D-glucopyranoside；methyl (2,3,4,6-tetra-O-(4-chlorobenzyl)-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-D-glucopyranoside；(2R,3R,4S,5R,6R)-3,4,5-tris[(4-chlorophenyl)methoxy]-2-[(4-chlorophenyl)methoxymethyl]-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]oxane
• 化学式: C₆₂H₆₂Cl₄O₁₁
• 分子量: 1124.98
• InChiKey: VEPQSVRMUFBOQV-KJBGKYNMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12
• 重原子数：
  77
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为产物：
  描述：

  甲基2,3,4-三-O-苄基-α-D-吡喃葡萄糖苷 、 2,3,4,6-tetra-O-p-chlorobenzyl-β-D-glucopyranosyl phenyl carbonate 在 calcium sulfate 、 TrB(C₆F₅)4 作用下， 以 二氯甲烷 为溶剂， 反应 9.0h， 以93%的产率得到methyl (2,3,4,6-tetra-O-(4-chlorobenzyl)-β-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  使用对氯苄基化糖基碳酸酯作为糖基供体的 1,2-反式糖苷的高立体选择性合成

  摘要：

  2,3,4,6-四-Op-氯苄基-β-D-吡喃葡萄糖基苯基碳酸酯作为一种稳定且易于使用的催化立体选择性合成1,2-反式糖苷的新方法可用的糖基供体。以良好的收率和高立体选择性制备了几种 β-D-吡喃葡萄糖苷。

  DOI：

  10.1246/cl.1998.635

文献信息

• Remote Electronic Effects by Ether Protecting Groups Fine-Tune Glycosyl Donor Reactivity
  作者：Mads Heuckendorff、Lulu Teressa Poulsen、Henrik H. Jensen

  DOI：10.1021/acs.joc.6b00528

  日期：2016.6.17

  para-substituted benzyl ether protecting groups affect the reactivity of glycosyl donors of the thioglycoside type with the N-iodosuccinimide/triflic acid promoter system. Having electron donating p-methoxy-benzyl ether (PMB) groups increased the reactivity of the donor in comparison to having electron withdrawing p-chloro (PClB) or p-cyanobenzyl ether (PCNB) protecting groups, which decreased the reactivity

  已经确定，对位取代的苄基醚保护基团影响硫代糖苷类型的糖基供体与N-碘琥珀酰亚胺/三氟乙酸促进剂系统的反应性。与具有吸电子对氯基（PClB）或对氰基苄基醚（PCNB）保护基相比，具有给电子的对甲氧基苄基醚（PMB）基增加了供体的反应性，从而降低了糖基给体的反应性相对于母体苄基醚（Bn）保护的糖基供体。这些发现被用于通过调节它们的反应性而在两个苄基化的葡萄糖基供体之间进行第一次武装-解除武装的偶联。另外，本发明描述了高效的钯催化的对氯苄基保护的硫代糖苷的多重氰化和甲氧基化。
• 1,2-<i>cis</i>-Selective glucosylation enabled by halogenated benzyl protecting groups
  作者：Dancan K. Njeri、Claude J. Pertuit、Justin R. Ragains

  DOI：10.1039/d0ob00373e

  日期：——

  Electron-withdrawing groups and Lewis basic solvent enable 1,2-cis-selectivity.

  电子吸引基团和路易斯碱性溶剂使1,2-cis-选择性成为可能。
• An extremely mild and stereocontrolled construction of 1,2-cis-α-glycosidic linkages via benzyl-protected glycopyranosyl diethyl phosphites
  作者：Hiroko Tanaka、Hiroki Sakamoto、Ai Sano、Seiichi Nakamura、Makoto Nakajima、Shunichi Hashimoto

  DOI：10.1039/a902845e

  日期：——

  A highly stereocontrolled 1,2-cis-α-glycosidation reaction under conditions mild enough for acid-labile alcohols has been developed using benzyl-protected glycopyranosyl diethyl phosphites as glycosyl donors in the presence of 2,6-di-tert-butylpyridinium iodide and tetrabutylammonium iodide.

  在 2,6-二叔丁基吡啶鎓碘化物和四丁基铵碘化物存在下，以苄基保护的吡喃糖基二乙基膦酸盐为糖基供体，开发出了一种高度立体可控的 1,2-顺式-δ-糖苷化反应，其条件温和，足以适用于酸亲和醇。
• Aryl(trifluoroethyl)iodonium Triflimide and Nitrile Solvent Systems: A Combination for the Stereoselective Synthesis of Armed 1,2-<i>trans</i>-β-Glycosides at Noncryogenic Temperatures
  作者：An-Hsiang Adam Chu、Andrei Minciunescu、Clay S. Bennett

  DOI：10.1021/acs.orglett.5b03282

  日期：2015.12.18

  Armed thioglycosides can be activated With aryl(trifluoroethyl)iodonium triflimide in 2:1 CH2Cl2/pivalonitrle or a solvent combination of CH2Cl2, acetonitrile, isobutyronitrile, and pivalonitrile (6:1:1:1) at 0 degrees C for glycosylation reactions that proceed in good yield and:moderate to excellent selectivity (up to 25:1 beta/alpha). Comparison to other common glycosylation promoters reveals that :both the Mixed!, solvent and the iodonium salt promoter are required for stereoselectivity.
• Highly Stereoselective Synthesis of 1,2-trans-Glycosides Using p-Chlorobenzylated Glycosyl Carbonate as Glycosyl Donor
  作者：Teruaki Mukaiyama、Kazuo Miyazaki、Hiromi Uchiro

  DOI：10.1246/cl.1998.635

  日期：1998.7

  A new and efficient method for catalytic stereoselective synthesis of 1,2-trans-glycosides was successfully established by use of 2,3,4,6-tetra-O-p-chlorobenzyl-β-D-glucopyranosyl phenyl carbonate as a stable and easily-available glycosyl donor. Several β-D-glucopyranosides were prepared in good yields with high stereoselectivities.

  2,3,4,6-四-Op-氯苄基-β-D-吡喃葡萄糖基苯基碳酸酯作为一种稳定且易于使用的催化立体选择性合成1,2-反式糖苷的新方法可用的糖基供体。以良好的收率和高立体选择性制备了几种 β-D-吡喃葡萄糖苷。