3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyltrichloroacetimidate | 83025-20-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyltrichloroacetimidate
• 英文别名: 3,4,6-tri-O-acetyl-2-azido-2-deoxy-alpha-d-galactopyranosyl trichloroacetimidate；[(2R,3R,4R,5R,6R)-3,4-diacetyloxy-5-azido-6-(2,2,2-trichloroethanimidoyl)oxyoxan-2-yl]methyl acetate
• CAS: 83025-20-1
• 化学式: C₁₄H₁₇Cl₃N₄O₈
• 分子量: 475.67
• InChiKey: NXSDPOSAOAWHFZ-RMPHRYRLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  136
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyltrichloroacetimidate 在 silica gel supported sulfuric acid 、 水 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 53.0h， 生成
  参考文献：
  名称：

  以对甲氧基苯基糖苷的形式， 从锈果普罗旺斯O34合成与O抗原重复单元有关的四糖和三糖†

  摘要：

  据报道，从Providencia rustigianii O34合成了与O抗原重复单元有关的四糖和三糖。目标寡糖的合成是通过对市售单糖进行合理的保护基操作，然后进行立体选择性糖基化，使用H 2 SO 4-硅胶进行三氯乙亚氨酸盐的活化以及与之结合来实现的。N-碘琥珀酰亚胺 用于硫糖苷活化。

  DOI：

  10.1039/c2ra22407k
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-2-azido-2-deoxy-β-D-galactopyranosyl acetate 在 碳酸氢铵 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyltrichloroacetimidate
  参考文献：
  名称：

  Synthesis and immunological study of a wall teichoic acid-based vaccine against E. faecium U0317

  摘要：

  A repeat unit of cell wall teichoic acids (WTA) isolated from E. faecium U0317 was chemically synthesized efficiently by a stepwise strategy. It was derivatized with a 5-aminopentanyl linker to facilitate conjugation with carrier proteins KLH and HSA. Immunological studies of the KLH conjugate 1 demonstrated that it could provoke robust immune responses and high titers of IgG antibodies, which could successfully recognize the synthesized WTA repeat unit 3. This result suggested that synthetic glycoconjugate 1 could be a promising vaccine candidate against E. faecium for further studies.

  DOI：

  10.1080/07328303.2017.1390576

文献信息

• Synthetic Studies on Glycopeptides Concerned with Defense Response of Plants. I. Syntheses of Supprescins A and B.
  作者：Takuya KANEMITSU、Yukio OGIHARA、Tadahiro TAKEDA

  DOI：10.1248/cpb.45.643

  日期：——

  Two glycopeptides, supprescins A and B, that suppress the production of pisatin, a phytoalexin of pea, were synthesized. In the synthesis of supprescin A, condensation of 3, 4, 6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyl trichloroacetimidate or its glycosidic β isomer with N-(carbobenzoxy)-L-seryl-O-benzyl-L-seryl-glycine methyl ester was carried out in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) to give the monoglycosyl tripeptide derivatives. For the synthesis of supprescin B, glycosylation of 2, 3, 4, 6-tetra-O-acetyl-α-D-galactopyranosyl bromide and 1, 2, 3, 6-tetra-O-benzoyl-α-D-galactopyranose was promoted by silver trifluoromethanesulfonate (AgOTf) to provide a disaccharide derivative. The coupling of diglycosyl imidate, 2, 3, 4, 6-tetra-O-acetyl-β-D-galactopyranosyl-(1→4)-3, 6-di-O-benzoyl-2-azido-2-deoxy-D-galactopyranosyl trichloroacetimidate, and N-(carbobenzoxy)-L-seryl-O-benzyl-L-seryl-glycyl-4-benzyl-L-aspartyl-5-benzyl-L-glutamyl-O-benzyl-L-threonine methyl ester in the presence of TMSOTf afforded the diglycosyl hexapeptide derivatives. Reduction, followed by N-acetylation, and then removal of the remaining protecting groups afforded the desired supprescin B.

  两种糖肽，抑制蛋白A和B，能够抑制豌豆中一种植物抗毒素——豌豆素的合成，它们已被制备出来。在制备抑制蛋白A的过程中，三甲基硅基三氟甲磺酸酯(TMSOTf)的存在下，将3,4,6-三-O-乙酰基-2-叠氮-2-脱氧-α-D-半乳糖吡喃糖基三氯乙酰亚胺酯或其糖苷β异构体与N-(羧基苄氧羰基)-L-丝氨酸-O-苄基-L-丝氨酰甘氨酸甲酯进行缩合反应，得到单糖基三肽衍生物。在制备抑制蛋白B的过程中，2,3,4,6-四-O-乙酰基-α-D-半乳糖吡喃糖基溴和1,2,3,6-四-O-苯甲酰基-α-D-半乳糖吡喃糖在三氟甲磺酸银(AgOTf)的促进下进行糖基化反应，生成二糖衍生物。在TMSOTf的存在下，将二糖基亚胺酯，2,3,4,6-四-O-乙酰基-β-D-半乳糖吡喃糖基-(1→4)-3,6-二-O-苯甲酰基-2-叠氮-2-脱氧-D-半乳糖吡喃糖基三氯乙酰亚胺酯与N-(羧基苄氧羰基)-L-丝氨酸-O-苄基-L-丝氨酰甘氨酰-4-苄基-L-天冬氨酰-5-苄基-L-谷氨酰-O-苄基-L-苏氨酸甲酯进行偶联反应，得到二糖基六肽衍生物。随后进行还原、N-乙酰化和剩余保护基团的去除，最终得到了所需的抑制蛋白B。
• Synthetic and immunological studies on trimeric MUC1 immunodominant motif antigen-based anti-cancer vaccine candidates
  作者：Mingjing Li、Fan Yu、Chao Yao、Peng George Wang、Yonghui Liu、Wei Zhao

  DOI：10.1039/c7ob02976d

  日期：——

  Therapeutic vaccines have been regarded as a very promising treatment modality against cancer. Tumor-associated MUC1 is a promising antigen for the design of antitumor vaccines. However, body's immune tolerance and low immunogenicity of MUC1 glycopeptides limited their use as effective antigen epitopes of therapeutic vaccines. To solve this problem, we chose the immune dominant region of MUC1 VNTRs

  治疗性疫苗被认为是一种非常有前途的抗癌治疗方法。肿瘤相关性MUC1是用于设计抗肿瘤疫苗的有前途的抗原。但是，人体的免疫耐受性和MUC1糖肽的低免疫原性限制了它们作为治疗性疫苗的有效抗原表位的用途。为了解决这个问题，我们选择了MUC1 VNTRs的免疫优势区域。我们设计并合成了其线性三价糖肽片段，并将其与BSA偶联。免疫学评估表明，基于糖基化MUC1的疫苗11诱导的抗体比未糖基化10的抗体具有更强的结合力。新型构建的抗原表位具有克服天然MUC1糖肽弱免疫原性的潜力，值得进一步研究。
• Synthesis of Glycocinnasperimicin D
  作者：Taihei Nishiyama、Yoshifumi Kusumoto、Ken Okumura、Kanako Hara、Shohei Kusaba、Keiko Hirata、Yukihiro Kamiya、Minoru Isobe、Keiji Nakano、Hiyoshizo Kotsuki、Yoshiyasu Ichikawa

  DOI：10.1002/chem.200901745

  日期：2010.1.11

  The first total synthesis of amino sugar antibiotic glycocinnasperimicin D (1) has been achieved by a convergent, three‐component coupling strategy. The key steps involve the Heck–Mizoroki reaction by using the iodophenyl glycoside 50 and acryl amide 32 to furnish the right core structure of 1, and the construction of the urea glycoside employing the reaction of glycosyl isocyanate 8 with amino sugar

  氨基糖抗生素糖皮质激素亚胺D（1）的第一个全合成方法是通过收敛的三组分偶联策略实现的。的关键步骤涉及通过使用碘苯基糖苷赫克-Mizoroki反应50和丙烯酰胺32，得到的右侧芯结构1，并采用糖基异氰酸酯的反应的尿素糖苷的结构8与氨基糖9。通过氧化异腈10制备异氰酸糖基酯8，在偶联事件中显示出极好的反应性。在合成过程中遇到的合成障碍导致了使用2-氨基-六吡喃糖的α-选择性路易斯酸催化的苯基糖基化过程的发展，以及一种不影响甲硅烷基醚的乙酰胺脱保护的方法。
• Capture of Uropathogenic<i>E. coli</i>by Using Synthetic Glycan Ligands Specific for the Pap-Pilus
  作者：Hailemichael O. Yosief、Alison A. Weiss、Suri S. Iyer

  DOI：10.1002/cbic.201200582

  日期：2013.1.21

  Synthetic glycoconjugates for capturing pathogens: Mono‐ and biantennary biotinylated glycoconjugates have been synthesized, and their ability to capture different E. coli strains (see graph) indicates that these molecules could be used to differentiate between different E. coli pathovars.

  用于捕获病原体的合成糖缀合物：已经合成了单天线和双天线生物素化糖缀合物，它们捕获不同大肠杆菌菌株的能力（见图）表明这些分子可用于区分不同的大肠杆菌病原体。
• A Study on the Influence of the Structure of the Glycosyl Acceptors on the Stereochemistry of the Glycosylation Reactions with 2-Azido-2-Deoxy-Hexopyranosyl Trichloroacetimidates
  作者：M. Belén Cid、Francisco Alfonso、Manuel Martín-Lomas

  DOI：10.1002/chem.200400746

  日期：2005.1.21

  relative influence of these factors is difficult to evaluate. For a given set of experimental conditions, the stereochemical course of these glycosylations depends on structural features of both glycosyl donor and glycosyl acceptor. It is a balance of these factors, where the structure of the glycosyl donor always plays a major role, which determines the stereochemistry of the coupling reaction. Therefore

  通过使用一系列手性肌醇衍生物作为糖基受体，研究了以2-叠氮基-2-脱氧-D-葡萄糖-和D-吡喃半乳糖基三氯乙酰亚氨酸酯作为糖基供体的糖基化的立体化学结果。糖基受体的绝对构型，构象和构象柔韧性的影响已通过在相似的预先建立的实验条件下使用不同的糖基供体进行了研究。尽管受体的结构可能在支配这些糖基化的立体化学中起一定作用，但结果表明，总的来说，这些因素的相对影响难以评估。对于给定的一组实验条件，这些糖基化的立体化学过程取决于糖基供体和糖基受体的结构特征。这些因素之间的平衡是糖基供体的结构始终起主要作用的地方，它决定了偶联反应的立体化学。因此，文献中报道的其中糖基受体的结构对于确定反应的立体化学至关重要的实施例构成了特别有利的情况，目前尚无进一步的概括。