β-D-Galp-(1→3)-β-D-GlcpNAc-1-SEt | 399035-92-8

• 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: β-D-Galp-(1→3)-β-D-GlcpNAc-1-SEt
• 英文别名: ethyl O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1->3)-4,6-O-benzylidene-2-deoxy-1-thio-2-trichloroacetamido-β-D-glucopyranoside；ethyl 4,6-O-benzylidene-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-2-trichloroacetamido-β-D-glucopyranoside
• CAS: 399035-92-8
• 化学式: C₃₁H₃₈Cl₃NO₁₄S
• 分子量: 787.066
• InChiKey: WASCYXKHWNDIER-ONGVDSMOSA-N

物化性质

• 沸点：
  790.8±60.0 °C(Predicted)
• 密度：
  1.45±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  50.0
• 可旋转键数：
  11.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  180.45
• 氢给体数：
  1.0
• 氢受体数：
  15.0

反应信息

• 作为反应物：
  描述：

  β-D-Galp-(1→3)-β-D-GlcpNAc-1-SEt 在 N-溴代丁二酰亚胺(NBS) 、 N-碘代丁二酰亚胺 、 D(+)-10-樟脑磺酸 、 sodium methylate 、 silver trifluoromethanesulfonate 、 barium carbonate 作用下， 以 甲醇 、 四氯化碳 、 二氯甲烷 、 乙腈 、 1,1,2,2-四氯乙烷 为溶剂， 反应 5.0h， 生成 8-azido-3,6-dioxaoctyl 6-bromo-2,6-dideoxy-2-trichloroacetamido-3-O-(4,6-O-p-methoxybenzylidene-β-D-galactopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  霍乱弧菌 O:139 的 O-PS 的偶联就绪下游二糖片段的合成。

  摘要：

  配备接头的二糖，8-amino-3,6-dioxaoctyl 2,6-dideoxy-2-acetamido-3-O-beta-D-galactopyranosyluronate-beta-D-glucopyranoside (10)，分八步合成：乙酰溴半乳糖和乙基 4,6-O-benzylidene-2-deoxy-2-trichloroacetamido-1-thio-beta-D-glucopyranoside。最后一个中间体 8-azido-3,6-dioxaoctyl 4-O-benzyl-6-bromo-2,6-dideoxy-2-trichloroacetamido-3-O-(苄基 2,3-二-O-苄基-β-D-吡喃半乳糖醛酸)-β-D-吡喃葡萄糖苷 (9) 的位置允许进一步构建分子，并最终构建完整的六糖。整体脱保护 (9-->10) 是通过在钯炭上催化氢解一步完成的。

  DOI：

  10.1016/j.carres.2011.02.011
• 作为产物：
  描述：

  ethyl 2-deoxy-2-N-trichloroacetamido-1-thio-β-D-glucopyranoside 在 camphor-10-sulfonic acid 、 silver trifluoromethanesulfonate 、 1,1,3,3-四甲基脲 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 生成 β-D-Galp-(1→3)-β-D-GlcpNAc-1-SEt
  参考文献：
  名称：

  Practical Synthesis of Building Blocks for Oligosaccharides Containing the β-d-Galp-(1→3)-β-d-GlcpNAc Motif

  摘要：

  An efficient, new pathway for the synthesis of the title sequence has been developed. The sequence has been obtained as a glycosyl donor, beta-D-Galp-(1 -> 3)-beta-D-GlcpNAc-1-SEt, or equipped with a linker (spacer) suitable for conjugation to other molecules, beta-D-Galp-(1 -> 3)-beta-D-GlcpNAc-1-(OCH2CH2)(3)N-3. Both disaccharides have been obtained in crystalline condition for the first time and fully characterized. The existing synthesis of the intermediate disaccharide glycosyl donor was improved by conducting the silver triflate mediated glycosylation under base-deficient conditions in the presence of 1,1,3,3-tetramethylurea and in the absence of molecular sieves.

  DOI：

  10.1055/s-0033-1340620

文献信息

• Towards the First Chemical Synthesis of the Hexasaccharide O-Antigen of Vibrio cholerae O139
  作者：Pavol Kováč、Shu-jie Hou、Deepak Sail

  DOI：10.1055/s-0031-1289876

  日期：2011.12

  The hexasaccharide O-antigen of Vibrio cholerae O139 was synthesized in its protected form from thioglycosides and glycosyl bromides as glycosyl donors by a stepwise and blockwise approach. The synthesis was designed to permit a global, one-step deprotection (H2, Pd/C). It allows the transformation of 15 functionalities in one operation, namely the removal of ten benzyl protecting groups, the removal of a trichloroethyl phosphate protecting group, the conversion of two N-trichloroacetyl into N-acetyl groups, a bromomethyl into a methyl group, and the conversion of an azido into an amino group.

  通过逐步和分块的方法，以硫代糖苷和溴化糖苷为糖基供体，合成了霍乱弧菌O139的六糖O抗原。该合成设计为一步整体脱保护（H2，Pd/C）。它允许在一次操作中转换15个官能团，即去除10个苄基保护基团，去除一个三氯乙基磷酸酯保护基团，将两个N-三氯乙酰基转化为N-乙酰基，将一个溴甲基转化为甲基，并将一个叠氮转化为氨基。
• Study of glycosylation with N-trichloroacetyl-d-glucosamine derivatives in the syntheses of the spacer-armed pentasaccharides sialyl lacto-N-neotetraose and sialyl lacto-N-tetraose, their fragments, and analogues
  作者：Andrei A. Sherman、Olga N. Yudina、Yury V. Mironov、Elena V. Sukhova、Alexander S. Shashkov、Vladimir M. Menshov、Nikolay E. Nifantiev

  DOI：10.1016/s0008-6215(01)00213-0

  日期：2001.11

  The syntheses of 2-aminoethyl glycosides of the pentasaccharides Neu5Ac-alpha (2 --> 3)-Gal-beta (3(1 --> 4)-GlcNAc-beta (3(1 --> 3)-Gal-beta (1 --> 4)-Glc and Neu5Ac-alpha (2 --> 3)-Gal-beta (1 --> 3)-GlcNAc-beta (1 --> 3)-Gal-beta (1 --> 4)-Glc, their asialo di-, tri-, and tetrasaccharide fragments, and analogues included a systematic study of glycosylation with variously protected mono- and disaccharide donors derived from N-trichloroacetyl-D-glucosamine of galactose, lactose, and lactosamine glycosyl acceptors bearing benzoyl protection around the OH group to be glycosylated. Despite the. low reactivity of these acceptors, stereo specificity and good to excellent yields were obtained with NIS-TfOH-activated thioglycoside donors of such type, or with AgOTf-activated glycosyl bromides, while other promotors, as well as a trichloroacetimidate donor, were less effective, and a beta -acetate donor was inactive. In NIS-TfOH-promoted glycosylation with the thioglycosides, the use of TfOH in catalytic amount led to rapid formation of the corresponding oxazoline, but the quantity of TfOH necessary for further efficient coupling with an acceptor depended on the reactivity of the donor, varying from 0.07 equiv for a 3,6-di-O-benzylated monosaccharide derivative to 2.1 equiv for a peracetylated disaccharide one. In the glycosylation products, the N-trichloroacetyl group was easily converted into N-acetyl by alkaline hydrolysis followed by N-acetylation. (C) 2001 Elsevier Science Ltd. All rights reserved.