phenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thiol-D-galactopyranoside | 197663-12-0

• 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: phenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thiol-D-galactopyranoside
• 英文别名: phenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thio-D-galactopyranoside；phenyl-3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thio-D-galactopyranoside；phenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thio-d-galactoside；[(2R,3R,4R,5R)-3,4-diacetyloxy-5-azido-6-phenylsulfanyloxan-2-yl]methyl acetate
• CAS: 197663-12-0
• 化学式: C₁₈H₂₁N₃O₇S
• 分子量: 423.447
• InChiKey: CNHKWRLCQYERSK-IHAUNJBESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  128
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  phenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thiol-D-galactopyranoside 在 Rh on carbon 、 palladium hydroxide - carbon 吡啶 、 2,6-二叔丁基-4-甲基吡啶 、 三氟甲磺酸酐 、 氢气 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 二氯甲烷 、 氢氟酸 、 乙酸乙酯 、 甲苯 为溶剂， 生成 N-芴甲氧羰基-O-beta-(2-乙酰氨基-2-脱氧-3,4,6-三-O-乙酰基-alpha-D-吡喃半乳糖基)-L-苏氨酸
  参考文献：
  名称：

  The effects of glycosylation on peptide backbone conformation

  摘要：

  DOI：

  10.1021/ja00061a053
• 作为产物：
  描述：

  3,4-O-isopropylidene-6-O-(1-methoxy-1-methylethyl)-1-thio-β-D-galactopyranoside 在 4-二甲氨基吡啶 、 camphor-10-sulfonic acid 、 溶剂黄146 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 12.0h， 生成 phenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thiol-D-galactopyranoside
  参考文献：
  名称：

  Mechanistic Studies and Methods To Prevent Aglycon Transfer of Thioglycosides

  摘要：

  Thioglycosides have been employed extensively for the synthesis of complex oligosaccharides, carbohydrate libraries, and mimetics of O-glycosides. While very useful, aglycon transfer is a problematic side reaction with thioglycosides. In this paper, a series of mechanistic studies are described. The aglycon transfer process is shown to affect both armed and disarmed thioglycosides, cause anomerization of the carbon-sulfur bond of a thioglycoside, and destroy the product of a glycosylation reaction. The results indicate that the aglycon transfer process can be a major problem for a wide range of thioglycosides. This side reaction is especially important to consider when carrying out complex reactions such as solid-phase glycosylations, one-pot or orthogonal multicomponent glycosylations, and construction of carbohydrate libraries. To prevent transfer, a number of modified aglycons were examined. The 2,6-dimethylphenyl ( DMP) aglycon was found to effectively block transfer in a variety of model studies and glycosylation reactions. The DMP group can be installed in one step from a commercially available thiol ( 2,6-dimethylthiophenol) and is useable as a glycosyl donor. On the basis of these features, the DMP group is proposed as a convenient and improved aglycon for thioglycosides.

  DOI：

  10.1021/ja063247q

文献信息

• Synthesis of Tn, Sialyl Tn and HIV-1-Derived Peptide Antigen Conjugates Having a Lipid A Analog as an Immunoadjuvant for Synthetic Vaccines.
  作者：Keisuke MIYAJIMA、Takahiro NEKADO、Kiyoshi IKEDA、Kazuo ACHIWA

  DOI：10.1248/cpb.46.1676

  日期：——

  Conjugates (3-5) of Tn, sialyl Tn and HIV-1-derived peptide antigen with a N-tetradecanoyl L-serine-β-alanine-containing D-glucosamine derivative, structurally related to lipid A, as an immunoadjuvant for the development of totally synthetic vaccines against cancers or HIV were synthesized. The mitogenic activity of compounds 3, 4 and 5 was stronger than that of lipid A analogs (1, 2).

  Tn 抗原、唾液酸 Tn 抗原和 HIV-1 来源的肽抗原与一种结构类似于脂多糖 A (lipid A) 的 N-十四烷酰-L-丝氨酸-β-丙氨酸-含 D-葡糖胺衍生物偶联物（3-5），被用作免疫佐剂，用于开发完全合成针对癌症或 HIV 的疫苗。化合物 3、4 和 5 的促有丝分裂活性均强于脂多糖 A 类似物（1 和 2）。
• An improved method for the synthesis of protected glycosyl fluorides from thioglycosides using N,N-diethylaminosulfur trifluoride (DAST)
  作者：Katsuhiko Suzuki、Yukishige Ito、Osamu Kanie

  DOI：10.1016/j.carres.2012.07.003

  日期：2012.10

  examined using N,N-diethylaminosulfur trifluoride (DAST). Although the reaction proceeded without N-bromosuccinimide (NBS), in some cases it was found that the electrophilicity of the Vilsmeier-type electrophilic sulfinium cation species was not sufficient for the activation of certain less-reactive thioglycosides. Here, we report the results of fluorination reactions of a series of monosaccharides using

  使用N，N-二乙基氨基三氟化硫（DAST）检查了硫糖苷直接转化为寡糖合成中常用的糖基氟化物。尽管反应在没有N-溴代琥珀酰亚胺（NBS）的情况下进行，但在某些情况下，发现Vilsmeier型亲电electro阳离子物种的亲电性不足以活化某些反应性较低的硫代糖苷。在这里，我们报告了在不存在NBS的情况下使用DAST进行的一系列单糖氟化反应的结果，并讨论了在存在二甲基（甲硫基）s三氟甲烷磺酸盐（DMTST）的情况下加速反应的过程，从而提高了产品收率。
• Synthesis of the tumor associative α-aminooxy disaccharide of the TF antigen and its conjugation to a polysaccharide immune stimulant
  作者：Jean Paul Bourgault、Kevin R. Trabbic、Mengchao Shi、Peter R. Andreana

  DOI：10.1039/c4ob00128a

  日期：——

  The α-aminooxy derivative of the Thomsen–Friedenriech tumor associated carbohydrate antigen has been synthesized in 11 steps utilizing a D-GalN3 acceptor carrying a pre-installed α-N-hydroxysuccinimidyl moiety. The natural α linkage was prepared in high selectivity employing a suitably protected D-GalN3-thioglycoside donor with N-hydroxysuccinimide. With access to α-TF-ONH2, the preparation of the

  Thomsen-Friedenriech 肿瘤相关糖类抗原的 α-氨基氧基衍生物是通过 11 个步骤合成的，使用带有预安装的 α- N-羟基琥珀酰亚胺基部分的D- GalN 3受体。使用适当保护的D- GalN 3 -硫糖苷供体和N-羟基琥珀酰亚胺以高选择性制备天然 α 键。随着α-TF-ONH 2的获得，TF-PS A1候选疫苗的制备通过肟键的形成顺利进行。
• In vitro synthesis of mucin-type O-glycans using saccharide primers comprising GalNAc-Ser and GalNAc-Thr residues
  作者：Ryuma Sakura、Kaori Nagai、Yuka Yagi、Yoshihisa Takahashi、Yoshimi Ide、Yuki Yagi、Daiki Yamamoto、Mamoru Mizuno、Toshinori Sato

  DOI：10.1016/j.carres.2021.108495

  日期：2022.1

  synthesized as saccharide primers to prime mucin-type O-glycan biosynthesis in cells. Upon incubating human gastric cancer MKN45 cells with the saccharide primers, 22 glycosylated products were obtained, and their structures were analyzed using liquid chromatography-mass spectrometry and enzyme digestion. The amounts of glycosylated products were dependent on the amino acid residues in the saccharide primers

  已知蛋白质中丝氨酸或苏氨酸残基的粘蛋白型O-糖基化是主要的翻译后修饰之一。在这项研究中，两种新型烷基糖苷，N α -lauryl - O -(2-acetamido-2-deoxy-α- d -galactopyranosyl ) -l -serineamide (GalNAc-Ser-C12) 和N α -lauryl - O- (2-acetamido-2-deoxy-α- d -galactopyranosyl ) -l -threonineamide (GalNAc-Thr-C12) 作为糖类引物合成O型粘蛋白-细胞中的聚糖生物合成。用糖类引物孵育人胃癌 MKN45 细胞后，获得了 22 种糖基化产物，并使用液相色谱-质谱法和酶消化法分析了它们的结构。糖基化产物的量取决于糖类引物中的氨基酸残基。例如，体外T 抗原 (Galβ1-3GalNAc)、岩藻糖基-T (Fucα1-2Galβ1-3GalNAc)
• [EN] GLYCOSYLATED ANTITUMOR ETHER LIPIDS AS NOVEL CANCER STEM CELL CYTOTOXIC AGENTS<br/>[FR] ÉTHER-LIPIDES ANTICANCÉREUX GLYCOSYLÉS EN TANT QUE NOUVEAUX AGENTS CYTOTOXIQUES DE CELLULES SOUCHES CANCÉREUSES
  申请人：UNIV MANITOBA

  公开号：WO2013116949A1

  公开（公告）日：2013-08-15

  Glycosylated antitumor ether lipids (GAELs) are effective cytotoxic agents against cancer stem cells. Furthermore, combining GAELs which kill cells by a caspase-independent pathway with agents that kill cells by apoptosis will lead to elimination of the differentiated tumor cells and the undifferentiated cancer stem cells leading to an elimination of the tumor and preventing recurrence.

  糖基化抗肿瘤醚脂质（GAELs）是有效的细胞毒性剂，可针对癌干细胞。此外，将通过一种与半胱氨酸蛋白酶无关的途径杀死细胞的GAELs与通过凋亡杀死细胞的药物结合，将导致消除分化的肿瘤细胞和未分化的癌干细胞，从而消除肿瘤并预防复发。