p-methoxyphenyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranoside | 140615-82-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-methoxyphenyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranoside
• 英文别名: para-methoxyphenyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl-(1-4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranoside；4-Methoxyphenyl 4-o-(3,6-di-o-benzyl-2-deoxy-2-phthalimido-beta-d-glucopyranosyl)-3,6-di-o-benzyl-2-deoxy-2-phthalimido-beta-d-glucopyranoside；2-[(2S,3R,4R,5S,6R)-2-[(2R,3S,4R,5R,6S)-5-(1,3-dioxoisoindol-2-yl)-6-(4-methoxyphenoxy)-4-phenylmethoxy-2-(phenylmethoxymethyl)oxan-3-yl]oxy-5-hydroxy-4-phenylmethoxy-6-(phenylmethoxymethyl)oxan-3-yl]isoindole-1,3-dione
• CAS: 140615-82-3
• 化学式: C₆₃H₅₈N₂O₁₄
• 分子量: 1067.16
• InChiKey: DJEDYDZKBLYAJG-ODVRWTDWSA-N

物化性质

• 密度：
  1.40±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  79
• 可旋转键数：
  21
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  178
• 氢给体数：
  1
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl-O-trichloroacetimidate 、 p-methoxyphenyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranoside 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 以73%的产率得到p-methoxyphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis and cytotoxic activity of the N-acetylglucosamine-bearing triterpenoid saponins

  摘要：

  Fourteen ursolic acid and oleanolic acid saponins with N-acetyl-beta-D-glucosamine, and (1 -> 4)-linked and (1 6)-linked N-acetyl-beta-D-glucosamine oligosaccharide residues were synthesized in a convergent manner. The structures of all compounds were confirmed by (1)H NMR and (13)C NMR spectroscopy and by mass spectrometry, and their cytotoxic activities were assayed in three cancer cell lines. Only oleanolic acid-3-yl beta-D-GluNAc showed significant cytotoxicity against HL-60 and BGC-823. (C) 2010 Published by Elsevier Ltd.

  DOI：

  10.1016/j.carres.2010.01.002
• 作为产物：
  描述：

  4-甲氧苯基-3,6-二-O-苄基-2-脱氧-2-苯二甲酰亚氨基-β-D-吡喃葡萄糖苷 在 三氟化硼乙醚 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成 p-methoxyphenyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranoside
  参考文献：
  名称：

  Stereocontrolled synthesis of chitosan dodecamer

  摘要：

  DOI：

  10.1016/0008-6215(93)84095-n

文献信息

• Preparation of Thiosugars and Their Use
  申请人：Davis Benjamin Guy

  公开号：US20090176970A1

  公开（公告）日：2009-07-09

  A process for the preparation of a thiosaccharide represented by Saccharide-S-H wherein Saccharide comprises at least 4 sugar units, comprises subjecting a corresponding compound of the formula (P)Saccharide-S-(P) wherein (P) represents an O- or S-protecting group(s), to Birch reduction.

  一种制备由糖硫代糖（Saccharide-S-H）表示的硫代糖的方法，其中糖代表至少4个糖单元，包括将具有以下结构的相应化合物（P）糖硫代糖（P）进行桦还原：（P）糖硫代糖（P），其中（P）代表一个或多个O-或S-保护基。
• Propargyl mediated intramolecular aglycon delivery (IAD): applications to the synthesis of core N-glycan oligosaccharides
  作者：Emanuele Attolino、Thomas W.D.F. Rising、Christoph D. Heidecke、Antony J. Fairbanks

  DOI：10.1016/j.tetasy.2007.06.026

  日期：2007.7

  and subsequent intramolecular glycosylation occurs with complete control of anomeric stereochemistry to form the Manβ(1→4)GlcNAc linkage. A variety of linear and convergent approaches (1+2, 3+1, 3+2) to the core pentasaccharide are investigated as means of probing the generality and limitations of this type of intramolecular aglycon delivery for the formation of β-mannoside linkages in complex oligosaccharides

  研究了炔丙基介导的分子内糖苷配基传递（IAD）用于合成N-聚糖寡糖（包括核心N-聚糖五糖）的关键Manβ（1→4）GlcNAc键的过程。甘露聚糖的2- O-炔丙基的异构化异戊二烯的硫代糖苷供体之后，是碘鎓离子介导的缩醛与受保护的GlcNAc受体的4-OH混合形成，随后发生分子内糖基化，且完全控制异头立体化学，形成Manβ（1→4）GlcNAc键。研究了五种核心五糖的线性和收敛方法（1 + 2、3 + 1、3 + 2），作为探索这种类型的分子内糖苷配基递送以形成β-甘露糖苷键的普遍性和局限性的手段复杂的低聚糖。
• Highly Optimized <i>β</i>-Mannosylation via <i>p</i>-Methoxybenzyl Assisted Intramolecular Aglycon Delivery
  作者：Yukishige Ito、Yuki Ohnishi、Tomoya Ogawa、Yoshiaki Nakahara

  DOI：10.1055/s-1998-1894

  日期：1998.10

  Highly efficient and stereoselective β-mannosylation was achieved by using mannosyl thioglycosides 5 and 19. Intramolecular aglycon delivery (IAD) from mixed acetal 12, 15 and 20, obtainable by oxidative coupling of aglycon onto mannosyl thio-glycosides which carry p-methoxybenzyl (PMB) group at C-2 position, was performed by the action of MeOSO2CF3 to afford β-mannosides 13/16/21. It is to be noted that efficiency of IAD was substantially improved by changing the protecting group at the 4- and 6-positions from previously utilized benzylidene to cyclohexylidene (5) or TIPDS (19) group. As a result, it is now possible to perform the β-manno glycosylation in a highly optimized manner to afford di- and trisaccharides with a backbone structure corresponding to asparagine-linked oligosaccharides in 75-85% yield as single stereoisomers.

  使用甘露糖基硫代糖苷 5 和 19 实现了高效和立体选择性δ-甘露糖基化。在 MeOSO2CF3 的作用下，混合缩醛 12、15 和 20 中的苷元通过氧化偶联到 C-2 位带对甲氧基苄基（PMB）的甘露糖基硫代糖苷上，实现了分子内苷元传递（IAD），从而得到δ-甘露糖苷 13/16/21。值得注意的是，通过将 4-位和 6-位的保护基团从之前使用的亚苄基改为亚环己基（5）或 TIPDS（19）基团，IAD 的效率大大提高。因此，现在有可能以高度优化的方式进行δ-甘露糖基化，以 75%-85% 的产率获得具有与天冬酰胺连接的低聚糖相对应的骨架结构的二糖和三糖单个立体异构体。
• On the Stereochemistry of Tethered Intermediates inp-Methoxybenzyl-Assisted β-Mannosylation
  作者：Matthias Lergenmüller、Tomoo Nukada、Koji Kuramochi、Akihito Dan、Tomoya Ogawa、Yukishige Ito

  DOI：10.1002/(sici)1099-0690(199906)1999:6<1367::aid-ejoc1367>3.0.co;2-n

  日期：1999.6

  under oxidative conditions followed by the activation of the anomeric position affords β-manno-glycoside as a single stereoisomer. Although the utility of this method has been further demonstrated in the synthesis of the core structure of Asn-linked glycan chains, there remained uncertainty with respect to the stereochemistry of the mixed acetal. In order to make a stereochemical assignment of this

  我们先前已经开发了立体控制合成β-甘露糖苷的新方法。从2- O- PMB（对甲氧基苄基）保护的甘露糖基供体1开始，在氧化条件下转化成混合的乙缩醛3，然后活化异头位置，得到β-甘露糖苷作为单一立体异构体。尽管在合成Asn连接的聚糖链的核心结构中已经进一步证明了该方法的实用性，但是关于混合乙缩醛的立体化学仍然存在不确定性。为了对该中间体进行立体化学分配，非对映体缩醛14a，15a和14B，15B是从制备9 + 10 / 7和11 + 12 / 13分别。借助NMR和使用DADAS 90的计算方法对空间位阻进行定量研究的结论是，由2 - O -PMB保护的9衍生的14a / 15a具有（S）构型，而从2- O衍生的14b / 15b -unprotected 11具有（R）配置。根据特点1固有的（H-NMR图案小号）异构体，4,6- ø -亚苄基保护的30 - 35，从thiomannoside
• Stereocontrolled synthesis of the pentasaccharide core structure of asparagine-linked glycoprotein oligosaccharide based on a highly convergent strategy
  作者：Akihito Dan、Yukishige Ito、Tomoya Ogawa

  DOI：10.1016/0040-4039(95)01604-x

  日期：1995.10

  A highly convergent synthesis of the Man3GlcNAc2 pentasaccharide structure 1 which is common to all asparagine-linked glycans is described. p-Methoxybenzyl assisted β-mannosidation was successfully applied to the coupling of trimannoside donor 3 and chitobiose derivative 4 to give the pentasaccharide 2 as a single isomer. Subsequent deprotection afforded the target compound 1.

  描述了Man 3 GlcNAc 2五糖结构1的高度收敛的合成，其对于所有天冬酰胺连接的聚糖都是共有的。对甲氧基苄基辅助的β-甘露糖苷化成功地用于三甘露糖苷供体3和壳二糖衍生物4的偶联，得到五糖2为单一异构体。随后的脱保护得到目标化合物1。