3,4,6-tri-O-benzyl-1,2-O-(exo-ethoxyethylidene)-α-D-glucopyranose | 158852-31-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 3,4,6-tri-O-benzyl-1,2-O-(exo-ethoxyethylidene)-α-D-glucopyranose
• 英文别名: 3,4,6-tri-O-benzyl-1,2-O-ethoxyethylidene-α-D-glucopyranose
• CAS: 158852-31-4
• 化学式: C₃₁H₃₆O₇
• 分子量: 520.623
• InChiKey: HWTIKERIIAXGDZ-YZTFKCKSSA-N

物化性质

• 沸点：
  611.1±55.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.22
• 重原子数：
  38.0
• 可旋转键数：
  12.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  64.61
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-1,2-O-(exo-ethoxyethylidene)-α-D-glucopyranose 在 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 4-methylphenyl 3,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Stereospecific Synthesis of 1,2-cis Glycosides by Vinyl-Mediated IAD

  摘要：

  (GRAPHICS)Stereospecific 1,2-cis glycosylation of 2-O-vinyl thioglycosides, synthesized from the corresponding alcohols by Ir-catalyzed transvinylation with vinyl acetate, is achieved by iodine-mediated tethering of a range of primary and secondary carbohydrate acceptors, followed by intramolecular aglycon delivery (IAD). The use of such an intramolecular glycosylation strategy furnishes the desired alpha-gluco and beta-manno disaccharides in an entirely stereoselective manner.

  DOI：

  10.1021/ol048427o
• 作为产物：
  描述：

  2,3,4,6-四乙酰氧基-alpha-D-吡喃葡萄糖溴化物 在 2,4,6-三甲基吡啶 、 氢氧化钾 、 四丁基溴化铵 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 3,4,6-tri-O-benzyl-1,2-O-(exo-ethoxyethylidene)-α-D-glucopyranose
  参考文献：
  名称：

  3,4,6-Tri-O-benzyl-.alpha.-D-arabino-hexopyranos-2-ulosyl Bromide: A Versatile Glycosyl Donor for the Efficient Generation of .beta.-D-Mannopyranosidic Linkages

  摘要：

  An expedient four-step sequence is described for the conversion of acetobromoglucose into the title 2-oxohexosyl (''ulosyl'') bromide 4. Due to its O-benzyl protection, 4 is considerably more reactive than its acylated analogs 1-3: Ag2CO3-promoted glycosidations with 2-propanol, diacetone-galactose, and methyl 2,3-O-isopropylidene-alpha-L-rhamnoside are complete within minutes and, in addition, are endowed with beta-specificity. This renders ulosyl bromide 4 a most propitious, indirect beta-D-mannosyl donor, inasmuch as the borohydride reduction of the beta-D-glycosiduloses formed (14-16 --> 19, 21, and 22) proceeds with manno selectivities of >20:1. Comparative evaluation of the manno/gluco ratios obtained in all 21 beta-D-arabino hexosidulose reductions (Table 1) reveals the 3-O-blocking group to have a pronounced effect on the outcome: >20:1 in cases with a 3-O-benzyl group versus only 2:1 to 3:1 in the presence of 3-O-acyl functions.

  DOI：

  10.1021/jo00101a035

文献信息

• Total Synthesis of Myrmekioside A, a Mono-<i>O</i>-alkyl-diglycosylglycerol from Marine Sponge<i>Myrmekioderma</i>sp.
  作者：Jun Zhang、Chunxia Li、Linlin Sun、Guangli Yu、Huashi Guan

  DOI：10.1002/ejoc.201500471

  日期：2015.7

  Myrmekioside A, which was isolated from the marine sponge Myrmekioderma sp. as a member of the family of natural mono-O-alkyl-diglycosylglycerols, and which has a strong reversion effect on the tumor cell morphology of ras-transformed cells at 5 μg/mL, was synthesized for the first time in 17 steps and 14 % overall yield. The β-glycosidic linkages in myrmekioside A were successfully constructed by

  Myrmekioside A，它是从海洋海绵 Myrmekioderma sp. 中分离出来的。作为天然单-O-烷基-二糖基甘油家族的一员，5 μg/mL对ras转化细胞的肿瘤细胞形态有很强的逆转作用，首次分17步和14步合成% 总产率。myrmekioside A 中的 β-糖苷键是通过使用三氯乙酰亚胺和硫代糖苷作为糖基供体的相邻基团参与方法成功构建的。甘油主链 C-2 处的 2R 绝对构型源自 (S)-1,2- 异丙基甘油 (8)。这种合成方法可能适用于制备其他具有不同糖和烷基链的桃金娘苷类似物，用于进一步的结构-活性关系研究。
• Stereoselective 1,2-cis Glycosylation of 2-O-Allyl Protected Thioglycosides
  作者：Mahmoud Aloui、David J. Chambers、Ian Cumpstey、Antony J. Fairbanks、Alison J. Redgrave、Christopher M. P. Seward

  DOI：10.1002/1521-3765(20020603)8:11<2608::aid-chem2608>3.0.co;2-4

  日期：2002.6.3

  intramolecular aglycon delivery (IAD), whereby a glycosyl acceptor is temporarily appended to a hydroxyl group of a glycosyl donor is an attractive method that can allow the synthesis of 1,2-cis glycosides in an entirely stereoselective fashion. 2-O-Allyl protected thioglycoside donors are excellent substrates for IAD, and may be glycosylated stereoselectively through a three-step reaction sequence. This sequence

  分子内糖苷配基递送（IAD）技术，其中将糖基受体暂时附加到糖基供体的羟基上，是一种有吸引力的方法，它可以以完全立体选择性的方式合成1,2-顺式糖苷。2-O-烯丙基保护的硫代糖苷供体是IAD的优异底物，可通过三步反应序列进行立体选择性糖基化。该序列由定量产生的烯丙基键异构化组成，以产生乙烯基醚，该乙烯基醚随后可以进行所需的糖基受体的N-碘代琥珀酰亚胺介导的束缚，以及随后的分子内糖基化，从而相应地产生α-葡糖苷或β-甘露糖苷。尽管一锅连接和糖基化的尝试因与过量糖基受体之间的竞争性分子间反应而受阻，这个问题可以通过使用过量的糖基供体简单地克服。烯丙基介导的IAD是其他IAD合成β-甘露糖苷的方法的一种广泛适用的实用替代方法，该方法同样适用于α-葡萄糖键。就施用的简便性和产率而言，这是有利的，此外，不需要糖基供体的环状4，6-保护。
• Concise Total Synthesis of Peyssonnoside A
  作者：Gleb A. Chesnokov、Karl Gademann

  DOI：10.1021/jacs.1c07135

  日期：2021.9.8

  sulfated diterpenoid glucoside with a unique 5/6/3/6 tetracyclic skeleton with a highly substituted cyclopropane ring deeply embedded into the structure. Herein, we report the first total synthesis of this natural product in a concise, efficient, scalable, and highly diastereoselective fashion. The aglucone peyssonnosol was synthesized in 21% overall yield after 15 steps, featuring a Simmons–Smith cyclopropanation

  Peyssonnoside A 是一种海洋来源的硫酸化二萜葡萄糖苷，具有独特的 5/6/3/6 四环骨架，结构中深深嵌入高度取代的环丙烷环。在此，我们以简洁、高效、可扩展和高度非对映选择性的方式首次全合成了这种天然产物。经过 15 个步骤，以 Simmons-Smith 环丙烷化和 Mukaiyama 水合为特征，完全由底物的空间结构控制，合成了配基 Peyssonnosol，总产率为 21%。
• Stereospecific Synthesis of 1,2-<i>cis</i> Glycosides by Allyl-Mediated Intramolecular Aglycon Delivery. 2. The Use of Glycosyl Fluorides
  作者：Ian Cumpstey、Antony J. Fairbanks、Alison J. Redgrave

  DOI：10.1021/ol016175a

  日期：2001.7.1

  [reaction: see text] Stereospecific 1,2-cis glycosylation of 2-O-allyl-protected glucosyl and mannosyl fluorides via a sequence of allyl isomerization, N-iodosuccinimide-mediated tethering, and intramolecular aglycon delivery (IAD) is reported. The use of fluoride as anomeric leaving group is advantageous in that tethering efficiencies can be increased for hindered aglycon alcohols by the use of extended reaction

  [反应：见正文]据报道，通过烯丙基异构化，N-碘代琥珀酰亚胺介导的束缚和分子内糖苷配基递送（IAD）的序列，2-O-烯丙基保护的葡萄糖基和甘露糖基氟化物的立体特异性1,2-顺式糖基化。使用氟化物作为端基异构离去基团是有利的，因为通过使用延长的反应时间而没有竞争性端基异构活化，可以提高对受阻糖苷醇的束缚效率。分子内糖基化以完全立体选择性的方式提供所需的α-葡萄糖苷和β-甘露糖苷。
• Allyl Protecting Group Mediated Intramolecular Aglycon Delivery (IAD) of Glycosyl Fluorides
  作者：Ian Cumpstey、Antony J. Fairbanks、Alison J. Redgrave

  DOI：10.1007/s007060200020

  日期：2002.4.1

  sequence of allyl isomerization, N-iodosuccinimide mediated tethering, and intramolecular aglycon delivery (IAD). Fluoride is advantageous as an anomeric leaving group since extended reaction times can be employed to tether hindered aglycon alcohols without competitive anomeric activation. Tin(II) chloride mediated intramolecular glycosylation furnishes the desired α-glucosides and β-mannosides in an

  2-O-烯丙基保护的葡萄糖基和甘露糖基氟化物的 立体特异性1,2- 顺式 糖基化可以 通过 一系列烯丙基异构化，N-碘代琥珀酰亚胺介导的束缚和分子内糖苷配基递送（IAD）实现。氟化物作为异头离去基团是有利的，因为延长的反应时间可用于束缚受阻的糖苷配基醇而没有竞争性的异头活化。氯化锡（II）介导的分子内糖基化反应以完全立体选择性的方式提供了所需的α-葡萄糖苷和β-甘露糖苷。