O-ethyl S-[methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosyl)onate] dithiocarbonate | 121512-94-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: O-ethyl S-[methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosyl)onate] dithiocarbonate
• 英文别名: O-ethyl S-[methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosyl)onate] dithiocarbonate；O-Ethyl S-[methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycero-D-galacto-non-2-ulopyranosid)onate] dithiocarbonate；methyl (2S,4S,5R,6R)-5-acetamido-4-acetyloxy-2-ethoxycarbothioylsulfanyl-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 121512-94-5
• 化学式: C₂₃H₃₃NO₁₃S₂
• 分子量: 595.646
• InChiKey: FFSWHKBJBFZYLG-GAQSFIOXSA-N

物化性质

• 熔点：
  102-104 °C(Solv: hexane (110-54-3); benzene (71-43-2))
• 沸点：
  670.8±55.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  39
• 可旋转键数：
  18
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  236
• 氢给体数：
  1
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  O-ethyl S-[methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosyl)onate] dithiocarbonate 在 甲磺酰溴 、 silver trifluoromethanesulfonate 、 二异丙胺 作用下， 以 吡啶 为溶剂， 反应 7.5h， 生成 methyl (2S,4S,5R,6R)-5-acetamido-4-acetyloxy-2-[(2R,3S,4S,5R,6S)-3,5-diacetyloxy-2-(acetyloxymethyl)-6-[(3R,4S,5R,6S)-4,5-diacetyloxy-6-(2-trimethylsilylethoxy)oxan-3-yl]oxyoxan-4-yl]oxy-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
  参考文献：
  名称：

  Synthesis of XylβCer, Galβ1−4XylβCer, NeuAcα2−3Galβ1−4XylβCer and the Corresponding Lactone and Lactam Trisaccharides

  摘要：

  2-(Trimethylsilyl)ethyl 2-O-benzoyl- and 2,3-di-O-acetyl-beta-D-xylopyranosides (12 and 14) were synthesized in high yields and subjected to glycosylation with various glycosyl donors. Galactosylation of 12 gave the xylose analogue of TMSEt lactoside (3), which was transformed into the glycosyl acceptor 19. Sialylation then gave the xylose analogue of G(M3) trisaccharide (5). The TMSEt glycosides 10, 25, and 32 were transformed into the corresponding trichloroacetimidates, which were used for glycosylation of an azidosphingosine derivative. The resulting sphingosyl glycosides were transformed into the title ceramides. Treatment of NeuAc alpha 2-3Gal beta 1-4Xyl beta Cer (5) with acetic acid gave the corresponding l''-2'-lactone 7. Glycosylation of 12 or 14 with a G(M4)-lactam donor (40) gave the xylose analogue of G(M3)-lactam (42). There was a 3-fold increase in the formation of GAG chains in the presence of 0.5 mu M Xyl beta Cer (2) in the medium.

  DOI：

  10.1021/jo970298k
• 作为产物：
  描述：

  (1S,2R)-1-((2R,3R,4S,6R)-3-acetamido-4,6-diacetoxy-6-(methoxycarbonyl)tetrahydro-2H-pyran-2-yl)propane-1,2,3-triyl triacetate 在 盐酸 、 乙酰氯 作用下， 以 乙醇 为溶剂， 生成 O-ethyl S-[methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosyl)onate] dithiocarbonate
  参考文献：
  名称：

  N-乙酰神经氨酸的2-硫代糖苷的立体选择性合成

  摘要：

  用苯硫酚，苯甲硫醇分别处理5-乙酰氨基-2,4,7,8,9-戊-O-乙酰基-3,5-二氧-β-d-甘油-d-半乳糖-2-壬基吡咯烷磺酸甲酯（1）和乙硫醇在三氟化硼醚化物的存在下给出相应的2-硫代-β-糖苷3-5。用硫酚分别处理（5-乙酰氨基-4,7,8,9-四-O-乙酰基-3,5-二氧-β-d-甘油-d-半乳糖-2-壬基吡喃糖基氯）onate（2）在N，N-二异丙基乙胺，O-乙基S-硫代碳酸钾和O-乙基S-硫代碳酸钾的存在下，得到相应的2-硫代-α-糖苷7、10和11，其中10被转化了在与N，N-二甲基甲酰胺-碘化钠加热下，将其转化成2-硫代α-糖苷乙酯9。将苯基2-硫代糖苷3和7转化为相应的砜。

  DOI：

  10.1016/0008-6215(89)80054-0

文献信息

• Study of Interhalogens/Silver Trifluoromethanesulfonate as Promoter Systems for High-Yielding Sialylations
  作者：Andréas Meijer、Ulf Ellervik

  DOI：10.1021/jo0262412

  日期：2002.10.1

  halide nucleophile rather than activating the interhalogen compound and, by increasing the amount of AgOTf from 1 to 1.5 equiv (with respect to IBr), the yield in the model reaction improved from 74% to 89%. A comparison of two different anomeric leaving groups showed that glycal formation can be minimized using a thiophenyl donor instead of xanthate. By combining these observations, we were able to increase

  我们研究了卤素/银三氟甲磺酸盐（IX / AgOTf）促进的糖基化，发现形成的氧碳鎓离子（例如来自具有或不具有参与基团的化合物）对卤代亲核试剂的敏感性差异。这些差异可以使用HSAB理论来解释。通过将该理论应用于唾液酸化反应，我们将模型反应的产率从使用ICl的高度不可预测的35-46％提高到了使用IBr的74％。我们还表明，银离子最主要的作用是降低卤化物亲核试剂的浓度，而不是活化卤素间化合物，并且通过将AgOTf的量从1当量提高到1.5当量（相对于IBr），可以提高模型反应从74％提高到89％。对两个不同的异头离去基团的比较表明，使用硫代苯基供体而不是黄药可以最小化糖基的形成。通过结合这些观察，我们能够将模型反应的产率提高到97％。
• Iodine Monochloride/Silver Trifluoromethanesulfonate (ICl/AgOTf) as a Convenient Promoter System for <i>O</i>-Glycoside Synthesis
  作者：Teddy Ercegovic、Andreas Meijer、Göran Magnusson、Ulf Ellervik

  DOI：10.1021/ol015547c

  日期：2001.3.1

  The novel promoter system iodine monochloride/silver trifluoromethanesulfonate (ICl/AgOTf) was evaluated with various thioglycoside donors and saccharide acceptors, and O-glycosides were obtained in 46-82% yield. Several practical advantages of the ICl/AgOTf system over known promoter systems were observed, such as convenient handling of the reagents and absence of byproducts related to N-succinimide

  用各种硫代糖苷供体和糖受体评估了新型的启动子系统一氯化碘/三氟甲磺酸银（IC1 / AgOTf），并以46-82％的产率获得了O-糖苷。观察到了ICl / AgOTf系统相对于已知启动子系统的一些实际优点，例如方便的试剂处理和不存在与N-琥珀酰亚胺有关的副产物。
• Dissecting the Influence of Oxazolidinones and Cyclic Carbonates in Sialic Acid Chemistry
  作者：Pavan K. Kancharla、Chandrasekhar Navuluri、David Crich

  DOI：10.1002/anie.201204400

  日期：2012.10.29

  At a moment′s notice: Thermal equilibration of 1 and mass spectral analysis of sialyl phosphates suggest that the 4O,5N‐oxazolidinone and the 4,5‐O‐carbonate systems influence the anomeric effect and the mechanisms of sialidation by virtue of their dipole moment in the mean plane of the pyranose ring. The electron‐withdrawing effect destabilizes 2 and promotes associative glycosylation mechanisms.

  即时通知: 1 的热平衡和磷酸唾液酸的质谱分析表明 4 O ,5 N-恶唑烷酮和 4,5- O-碳酸酯系统通过以下方式影响异头效应和唾液酸化机制它们在吡喃糖环的平均平面上的偶极矩。吸电子效应使2不稳定并促进缔合糖基化机制。TEMPO=2,2,6,6-四甲基哌啶N-氧化物。
• Synthesis of Tn and sialyl Tn building blocks for solid phase glycopeptide synthesis
  作者：Mikael Elofsson、Jan Kihlberg

  DOI：10.1016/0040-4039(95)01515-9

  日期：1995.10

  blocks for direct use in Fmoc solid phase glycopeptide synthesis have been prepared in 3 and 5 steps, respectively, from p-cresyl 2-azido-2-deoxy-3,6-di-O-tert-butyldimethylsilyl-1-thio-β-D-galactopyranoside (3). The silyl protective groups used for the GalNAc moiety of the Tn building block may be removed simultaneously with glycopeptide cleavage from the solid phase under acidic conditions.

  TN（GalNAcα1→ Ò -Thr）和唾液酸Tn（NeuAcα2→6GalNAcα1→ ö -Thr）在3层5的步骤，分别制备了用于在Fmoc固相合成的糖肽直接使用积木，从p -cresyl 2-叠氮基2-脱氧-3，6-二-O-叔丁基二甲基甲硅烷基-1-硫代-β-D-吡喃半乳糖苷（3）。可以在酸性条件下与糖肽从固相上裂解同时除去用于Tn结构单元的GalNAc部分的甲硅烷基保护基。
• Solid-Phase Synthesis of a Sialyl-Tn-Glycoundecapeptide of the MUC1 Repeating Unit
  作者：Beate Liebe、Horst Kunz

  DOI：10.1002/hlca.19970800511

  日期：1997.8.11

  The synthesis of glycopeptides carrying tumour-associated antigens is of interest for cancer diagnosis and treatment. Here, a very efficient route lo disaccharide threonine building block 8 is presented which allows the introduction of the sialyl-Tn antigen into a peptide. The syntheses of the undecapeptide and the sialyl-Tn-containing glycoundecapeptide, which are a part of the repeating unit of MUC1

  携带肿瘤相关抗原的糖肽的合成对于癌症的诊断和治疗很重要。在此，提出了非常有效的二糖苏氨酸构建模块8的途径，其允许将唾液酸-Tn抗原引入肽中。作为MUC1重复单元的一部分的十一肽和含唾液酸基-Tn的糖十一肽的合成，是通过固相合成并利用在中性条件下可裂解的烯丙基锚进行的。从树脂上脱离后，肽和糖肽完全脱保护，分别得到目标化合物13和15。