[methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosonoate]-(2->6)-4-O-acetyl-2-azido-3-O-benzyl-2-deoxy-D-galactopyranosyl trichloroacetimidate | 1021159-74-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosonoate]-(2->6)-4-O-acetyl-2-azido-3-O-benzyl-2-deoxy-D-galactopyranosyl trichloroacetimidate
• CAS: 1021159-74-9
• 化学式: C₃₇H₄₆Cl₃N₅O₁₈
• 分子量: 955.154
• InChiKey: BNAJNEKXGIFVNG-ASPUXDNCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  63.0
• 可旋转键数：
  18.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  305.66
• 氢给体数：
  2.0
• 氢受体数：
  20.0

反应信息

• 作为反应物：
  描述：

  [methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosonoate]-(2->6)-4-O-acetyl-2-azido-3-O-benzyl-2-deoxy-D-galactopyranosyl trichloroacetimidate 、 N-叔丁氧羰基-L-丝氨酸 在 三氟甲磺酸三甲基硅酯 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以69%的产率得到N-tert-butoxycarbonyl O-[methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosonoate]-(2->6)-[4-O-acetyl-2-azido-3-O-benzyl-2-deoxy-α-D-galactopyranosyl]-L-serine benzyl ester
  参考文献：
  名称：

  Efficient Synthesis of MUC4 Sialylglycopeptide through the New Sialylation Using 5-Acetamido-Neuraminamide Donors

  摘要：

  Sialylation reactions using a new sialyl donor, diethyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy2-O-beta-D-glycero-D-galacto-2-nonulopyranosylonamide phosphite (Neu5Ac-l-amide-2-phosphite) derivatives, and the synthesis of the sialyl-T-N-MUC4 glycopeptide are described. The sialylation was performed in CH2Cl2 solvent toward the 6-hydroxyl group of several monosugar acceptors and generated alpha-sialoside in good yield under low temperature and TMSOTf activation system. Amide derivatives of sialoside were easily converted into naturally occurring sialoside after hydrolysis of the amide group. Sialyl-alpha(2,6)-GalN(3) was also prepared by this new sialylation protocol, and then this sialoside was further converted into a Fmoc-protected sialyl-T-N serine derivative for solid-phase glycopeptides synthesis. The solid-phase glycopeptide synthesis using this sialyl-T-N serine derivative in which the sugar hydroxyl group was free afforded the target sialyl-T-N-MUC4 glycopeptide.

  DOI：

  10.1021/jo702609p
• 作为产物：
  描述：

  [methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosonoate]-(2->6)-4-O-acetyl-2-azido-3-O-benzyl-2-deoxy-D-galactopyranoside 、 三氯乙腈 在 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以94%的产率得到[methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosonoate]-(2->6)-4-O-acetyl-2-azido-3-O-benzyl-2-deoxy-D-galactopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Efficient Synthesis of MUC4 Sialylglycopeptide through the New Sialylation Using 5-Acetamido-Neuraminamide Donors

  摘要：

  Sialylation reactions using a new sialyl donor, diethyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy2-O-beta-D-glycero-D-galacto-2-nonulopyranosylonamide phosphite (Neu5Ac-l-amide-2-phosphite) derivatives, and the synthesis of the sialyl-T-N-MUC4 glycopeptide are described. The sialylation was performed in CH2Cl2 solvent toward the 6-hydroxyl group of several monosugar acceptors and generated alpha-sialoside in good yield under low temperature and TMSOTf activation system. Amide derivatives of sialoside were easily converted into naturally occurring sialoside after hydrolysis of the amide group. Sialyl-alpha(2,6)-GalN(3) was also prepared by this new sialylation protocol, and then this sialoside was further converted into a Fmoc-protected sialyl-T-N serine derivative for solid-phase glycopeptides synthesis. The solid-phase glycopeptide synthesis using this sialyl-T-N serine derivative in which the sugar hydroxyl group was free afforded the target sialyl-T-N-MUC4 glycopeptide.

  DOI：

  10.1021/jo702609p

文献信息

• Efficient Substitution Reaction from Cysteine to the Serine Residue of Glycosylated Polypeptide: Repetitive Peptide Segment Ligation Strategy and the Synthesis of Glycosylated Tetracontapeptide Having Acid Labile Sialyl-T_N Antigens
  作者：Ryo Okamoto、Shingo Souma、Yasuhiro Kajihara

  DOI：10.1021/jo8026164

  日期：2009.3.20

  This paper reports the synthesis of a 40-residue glycopeptide having two antigenic sialyl-TN (NeuAc-α-(2,6)-GalNAc-Thr) residues in the MUC1 sequence. This target glycopeptide is a tandem repeat form of 20-residue glycopeptides. For the synthesis of this large molecule, native chemical ligation (NCL) at the serine site was used (CysNCLSer). The concept of CysNCLSer relies on the following: (1) conventional

  本文报道了40个残基的糖肽的合成，该肽在MUC1序列中具有两个抗原性唾液酸-T N（NeuAc-α-（2,6）-GalNAc-Thr）残基。该靶糖肽是20残基糖肽的串联重复形式。为了合成该大分子，使用了丝氨酸位点的天然化学连接（NCL）（Cys NCL Ser）。Cys NCL Ser的概念依赖于以下内容：（1）肽-α-硫酯与另一个肽段的半胱氨酸残基之间的常规NCL；（2）用于NCL的硫醇的甲基化；（3）半胱氨酸残基向丝氨酸残基的酸性CNBr转化，形成O-酯键；和（4）的直径： -到N-酰基转移以通过天然酰胺键偶联两个糖肽。为了合成具有酸不稳定糖部分的糖肽，通过固相糖肽合成来合成在N末端具有半胱氨酸残基的20残基糖肽-α-硫酯和2​​0残基糖肽，然后通过Cys NCL Ser偶联。作为广泛研究的结果，发现用额外的酸（三氟乙酸）进行CNBr活化对于获得良好的反应性和产率至关重要，该条件提供了具有两个唾液酸-T