ethyl 4,6-O-benzylidene-2-deoxy-1-thio-2-trichloroacetamido-β-D-glucopyranoside | 399035-88-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: ethyl 4,6-O-benzylidene-2-deoxy-1-thio-2-trichloroacetamido-β-D-glucopyranoside
• 英文别名: ethyl 4,6-O-benzyliden-2-deoxy-2-N-trichloroacetamido-thio-β-D-glucopyranoside；ethyl 2-trichloroacetamido-2-deoxy-4,6-O-benzylidene-1-thio-β-D-glucopyranoside；ethyl 4,6-O-benzylidene-2-deoxy-2-trichloroacetamido-1-thio-β-D-glucopyranoside；ethyl 4,6-O-benzylidene-2-deoxy-2-N-trichloroacetamido-1-thio-β-D-glucopyranoside；N-[(2R,4aR,6S,7R,8R,8aS)-6-ethylsulfanyl-8-hydroxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]-2,2,2-trichloroacetamide
• CAS: 399035-88-2
• 化学式: C₁₇H₂₀Cl₃NO₅S
• 分子量: 456.774
• InChiKey: OTLWPDCZBXBWEN-OJVARPOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  102
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 4,6-O-benzylidene-2-deoxy-1-thio-2-trichloroacetamido-β-D-glucopyranoside 在 三氯化铝 、 硼烷-三甲胺络合物 、 水 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.5h， 生成 ethyl 3,6-di-O-benzyl-2-deoxy-1-thio-2-trichloroacetamido-β-D-glucopyranoside
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/s0008-6215(01)00213-0
• 作为产物：
  描述：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-trichloroacetamido-β-D-glucopyranose 在 camphor-10-sulfonic acid 、 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成 ethyl 4,6-O-benzylidene-2-deoxy-1-thio-2-trichloroacetamido-β-D-glucopyranoside
  参考文献：
  名称：

  硫酸皮肤素寡糖的模块化自动固相合成。

  摘要：

  硫酸皮肤素是糖胺聚糖多糖，其作为细胞外基质的一部分具有多种生物学作用。正交保护的D-半乳糖胺和L-艾杜糖醛酸结构单元以及可光裂解的接头对于硫酸皮肤素寡糖的自动合成至关重要。以高收率获得了易于结合的寡糖。

  DOI：

  10.1039/c3cc48860h

文献信息

• TMSOTf-Catalyzed Silylation: Streamlined Regioselective One-Pot Protection and Acetylation of Carbohydrates
  作者：A. Abragam Joseph、Ved Prakash Verma、Xin-Yi Liu、Chia-Hui Wu、Vijay M. Dhurandhare、Cheng-Chung Wang

  DOI：10.1002/ejoc.201101267

  日期：2012.2

  A highly efficient TMSOTf-catalyzed HMDS silylation of sugars, which can easily be integrated with subsequent reactions in one-pot fashion, has been developed. Its usefulness was demonstrated by applications to streamlined regioselective one-pot protection and nonenzymatic acetylation of un

  已经开发出一种高效的 TMSOTf 催化的 HMDS 糖基硅烷化，它可以很容易地以一锅法与后续反应相结合。其在简化区域选择性一锅法保护和非酶乙酰化方面的应用证明了其有用性。
• Automated glycan assembly of peptidoglycan backbone fragments
  作者：Pietro Dallabernardina、Valentina Benazzi、Jon D. Laman、Peter H. Seeberger、Felix F. Loeffler

  DOI：10.1039/d1ob01987b

  日期：——

  The automated glycan assembly of different oligosaccharide fragments of the bacterial peptidoglycan backbone is reported.

  报道了细菌肽聚糖骨架不同寡糖片段的自动糖基组装。
• Chemical Synthesis of the Galacturonic Acid Containing Pentasaccharide Antigen of the O-Specific Polysaccharide of <i>Vibrio cholerae</i> O139 and Its Five Fragments
  作者：Xiaowei Lu、Pavol Kováč

  DOI：10.1021/acs.joc.6b01019

  日期：2016.8.5

  Three pentasaccharides, two tetrasaccharides, and a trisaccharide fragment of the O-specific antigen of Vibrio cholerae O139 were synthesized by applying 1 + 1, 2 + 1, 3 + 1, and 4 + 1 coupling strategies. The most challenging tasks involved were the synthesis of the 1,2-cis-glycosidic linkage between galactose and the linker (spacer) molecule and final purification of the target multicharged substances

  霍乱弧菌O139的O特异抗原的三个五糖，两个四糖和一个三糖片段通过应用1 +1、2 +1、3 +1和4 +1偶联策略合成。涉及的最具挑战性的任务是半乳糖与接头（间隔子）分子之间的1,2-顺式-糖苷键的合成以及目标多电荷物质的最终纯化。通过用半乳糖醛酸的存在引起的加氢/氢解最终通过脱氢/氢解最终脱保护的困难通过用对氢处理呈惰性的基团保护该酸来克服。在结晶条件下获得了一些先前描述为不完全表征的非晶态材料的中间体，并首次对其进行了完全表征。
• Synthesis of the conjugation ready, downstream disaccharide fragment of the O-PS of Vibrio cholerae O:139
  作者：Shujie Hou、Pavol Kováč

  DOI：10.1016/j.carres.2011.02.011

  日期：2011.9

  The linker-equipped disaccharide, 8-amino-3,6-dioxaoctyl 2,6-dideoxy-2-acetamido-3-O-beta-D-galactopyranosyluronate-beta-D-glucopyranoside (10), was synthesized in eight steps from acetobromogalactose and ethyl 4,6-O-benzylidene-2-deoxy-2-trichloroacetamido-1-thio-beta-D-glucopyranoside. The hydroxyl group present at C-4(II) in the last intermediate, 8-azido-3,6-dioxaoctyl 4-O-benzyl-6-bromo-2,6-d

  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。
• Total Synthesis of the Complete Protective Antigen of<i>Vibrio cholerae</i>O139
  作者：Sameh E. Soliman、Pavol Kováč

  DOI：10.1002/anie.201606116

  日期：2016.10.4

  The first chemical synthesis of the complete protective O‐antigen of a human‐disease‐causing pathogenic bacterium is described. The synthesis involved a protecting‐group strategy that facilitated the regioselectivity of the key transformations, stereoselective glycosylation reactions, and enabled the one‐step global deprotection of the completely assembled, fully protected, phosphorylated hexasaccharide

  描述了引起人类疾病的致病细菌的完整保护性O抗原的首次化学合成。合成涉及保护基团策略，该策略可促进关键转化的区域选择性，立体选择性糖基化反应，并通过氢化/氢解作用对完全组装的，完全保护的磷酸化六糖进行一步全局脱保护。获得了最终的具有氨基官能团的，带有连接子的抗原，其形式可与合适的载体（例如蛋白质）偶联，以产生免疫原。