methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2,6-anhydro-D-glycero-D-galacto-non-2-enonate | 108812-69-7

• 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: methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2,6-anhydro-D-glycero-D-galacto-non-2-enonate
• 英文别名: methyl (2R,3R,4S)-3-acetamido-4-acetyloxy-2-[(1R,2R)-1,2,3-triacetyloxypropyl]-3,4-dihydro-2H-pyran-6-carboxylate
• CAS: 108812-69-7
• 化学式: C₂₀H₂₇NO₁₂
• 分子量: 473.434
• InChiKey: UZTLYEOULACYKZ-SXXASDTRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  33
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  170
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2,6-anhydro-D-glycero-D-galacto-non-2-enonate 生成 methyl (2R,3R,4R,5S,6R)-5-acetamido-4-acetyloxy-3-iodo-2-methoxy-6-[(1R,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
  参考文献：
  名称：

  KIRCHNER, ELKE;THIEM, FRAUKE;DERNICK, RUDOLF;HEUKESHOVEN, JOCHEN;THIEM, J+, J. CARBOHYDR. CHEM., 7,(1988) N 2, 453-486

  摘要：

  DOI：
• 作为产物：
  描述：

  (2R,4S,5R,6R)-5-acetamido-2,4-diacetyloxy-6-[(1R,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylic acid 在 三氟甲磺酸三甲基硅酯 作用下， 以 四氢呋喃 、 乙醚 、 乙腈 为溶剂， 反应 3.0h， 生成 methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2,6-anhydro-D-glycero-D-galacto-non-2-enonate
  参考文献：
  名称：

  Zbiral, Erich; Brandstetter, Hannelore H.; Christian, Rudolf, Liebigs Annalen der Chemie, 1987, p. 781 - 786

  摘要：

  DOI：

文献信息

• Regio/Stereoselective Glycosylation of Diol and Polyol Acceptors in Efficient Synthesis of Neu5Ac-α-2,3-LacNPhth Trisaccharide
  作者：Ying Zhang、Fu-Long Zhao、Tao Luo、Zhichao Pei、Hai Dong

  DOI：10.1002/asia.201801486

  日期：2019.1.4

  was developed. First, the regio/stereoselective glycosylation between glycoside donors and glucoNPhth diol acceptors was investigated. It was found that the regioselectivity depends not only on the steric hindrance of the C2‐NPhth group and the C6‐OH protecting group of the glucosamine acceptors, but also on the leaving group and protecting group of the glycoside donors. Under optimized conditions, LacNPhth

  开发了Neu5Ac-α-2,3-LacNPhth三糖衍生物的简便方法。首先，研究了糖苷供体和葡萄糖NPhth二醇受体之间的区域/立体选择性糖基化。发现区域选择性不仅取决于葡糖胺受体的C2-NPhth基团和C6-OH保护基的空间位阻，还取决于糖苷供体的离去基团和保护基。在优化条件下，LacNPhth衍生物在高达92％的产率通过全乙酰-α-D-吡喃半乳糖三氯之间的区域选择性/立体选择性糖基化合成p -甲氧基苯基6- ö -叔-butyldiphenylsilyl -2-脱氧-2-苯二甲酰亚-β- d-吡喃葡萄糖苷，避免形成糖基化原酸酯和异头糖苷配基。然后，将LacNPhth衍生物脱酰基，然后通过TBDPS保护在伯位置上，以形成LacNPhth多元醇受体。最后，通过LacNPhth多元醇受体与亚磷酸唾液酸基酯供体之间的区域/立体选择性糖基化反应，以48％的产率合成了Neu5Ac-α-2,3-La
• Systematic study on free radical hydrothiolation of unsaturated monosaccharide derivatives with exo- and endocyclic double bonds
  作者：László Lázár、Magdolna Csávás、Ádám Hadházi、Mihály Herczeg、Marietta Tóth、László Somsák、Terézia Barna、Pál Herczegh、Anikó Borbás

  DOI：10.1039/c3ob40547h

  日期：——

  reacted with various thiols by irradiation with UV light in the presence of a cleavable photoinitiator. The photoinduced radical-mediated hydrothiolation reactions showed highly varying overall conversions depending not only on the substitution pattern and electron-density of the double bond but also on the nature and substitution pattern of the thiol partner. Out of the applied thiols thiophenol, producing

  通过在可裂解的光引发剂的存在下用紫外线照射，使糖的外环和内环双键以及烯键的末端双键与各种硫醇反应。光诱导的自由基介导的氢硫醇化反应显示出很大变化的总转化率，这不仅取决于双键的取代方式和电子密度，还取决于硫醇配偶体的性质和取代方式。在所施加的硫醇中，产生高度稳定的噻吩基的硫酚对每种烯烃的反应性最低。在大多数情况下，氢硫醇化反应具有完全的区域选择性和立体选择性。将1,2：3,4-二-O-异亚丙基-6-硫代-α- D-吡喃半乳糖成功添加到2,3-不饱和N-乙酰神经氨酸衍生物提供（3→6）-S连接的假二糖，表明带有吸电子取代基的Neu5Ac-2-ene的内环双键在光诱导的硫醇-烯偶联反应中显示出足够的反应性。 。
• A New Method for the Synthesis of Fluoro-Carbohydrates and Glycosides Using Selectfluor
  作者：Michael D. Burkart、Zhiyuan Zhang、Shang-Cheng Hung、Chi-Huey Wong

  DOI：10.1021/ja9723904

  日期：1997.12.1

  This paper describes a high-yield, one-step synthesis of 2-deoxy-2-fluoro sugars and their glycosides from glycals using the available electrophilic fluorination reagent 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) in the presence of a nucleophile. The method was further expanded to the synthesis of glycosyl fluorides and glycosides from anomeric hydroxy

  本文描述了使用现有的亲电氟化试剂 1-氯甲基-4-氟-1,4-二氮杂二环[2.2.2] 从糖醛中高产、一步合成 2-脱氧-2-氟糖及其糖苷的方法辛烷双（四氟硼酸盐）（Selectfluor）在亲核试剂存在下。该方法进一步扩展到从异头羟基或硫糖苷衍生物合成糖基氟和糖苷。
• SnCl₄-catalyzed solvent-free acetolysis of 2,7-anhydrosialic acid derivatives
  作者：Kesatebrhan Haile Asressu、Cheng-Chung Wang

  DOI：10.3762/bjoc.15.295

  日期：——

  synthesized and subjected to different Lewis acid-catalyzed solvent-free ring-opening reactions at room temperature in the presence of acetic anhydride. Among the various Lewis acids tested, the desired acetolysis products were obtained in moderate yields under tin(IV) chloride catalysis. Our methodology could be extended to regioselective protecting group installations and manipulations towards a number of

  含有唾液酸的聚糖以不同的唾液酸形式和在生物活性糖缀合物中的各种糖苷键被发现。因此，为了获得纯净形式的聚糖，需要高度重视适当保护的唾液酸基砌块的制备。据此，合成了同时带有给电子和吸电子保护基的各种C-5-取代的2,7-脱水唾液酸衍生物，并在室温下于室温下进行了不同的路易斯酸催化的无溶剂开环反应。乙酸酐的存在。在测试的各种路易斯酸中，在氯化锡（IV）催化下以中等收率获得了所需的乙酰分解产物。
• Synthesis of Sialidase-Resistant Oligosaccharide and Antibody Glycoform Containing α2,6-Linked 3F^ax-Neu5Ac
  作者：Hong-Jay Lo、Larissa Krasnova、Supriya Dey、Ting Cheng、Haitian Liu、Tsung-I Tsai、Kevin Binchia Wu、Chung-Yi Wu、Chi-Huey Wong

  DOI：10.1021/jacs.9b01991

  日期：2019.4.24

  Fluorinated glycosides are known to resist the glycosidase-catalyzed glycosidic bond cleavage; however, the synthesis of such glycans, especially 3-fluoro-sialic acid (3F-Neu5Ac) containing sialosides, has been a major challenge. Though the enzymatic synthesis of alpha-2,3-linked 3F-sialosides was reported, until recently there has not been any effective method available for the synthesis of 3F-sialosides in the a-2,6-linkage. In order to understand the biological effect of such modification, we report here a chemical synthesis of 3F(ax)-Neu5Ac-alpha 2,6-Gal as a building block for the assembly of 3Fm-Neu5Ac-containing sialosides and a representative homogeneous antibody glycoform. Our results showed that the sialosides are stable under sialidase catalysis and the rituximab glycoform with a sialylated complex-type biantennary glycan terminated with 3F(ax)-Neu5Ac in the alpha-2,6-linkage (alpha 2,6-F-SCT) has a similar binding avidity as its parent glycoform. These findings open up new opportunities for the development of therapeutic glycoproteins with improved pharmacokinetic parameters.