1,3,6-tri-O-acetyl-4-O-(2',3',4',6'-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-2-iodo-α-D-manno-pyranose | 188426-22-4

• 英文名称: 1,3,6-tri-O-acetyl-4-O-(2',3',4',6'-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-2-iodo-α-D-manno-pyranose
• 英文别名: 1,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-2-iodo-α-D-mannopyranose；Gal2Ac3Ac4Ac6Ac(b1-4)a-Man1Ac2I3Ac6Ac；[(2R,3R,4S,5S,6R)-4,6-diacetyloxy-5-iodo-3-[(2S,3R,4S,5S,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxyoxan-2-yl]methyl acetate
• CAS: 188426-22-4
• 化学式: C₂₆H₃₅IO₁₇
• 分子量: 746.458
• InChiKey: OFSLTBJMMQUWQJ-SURUERECSA-N

物化性质

• 熔点：
  59 °C
• 沸点：
  679.2±55.0 °C(Predicted)
• 密度：
  1.55±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  44
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  212
• 氢给体数：
  0
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  1,3,6-tri-O-acetyl-4-O-(2',3',4',6'-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-2-iodo-α-D-manno-pyranose 在 吡啶 、 三氟甲磺酸三甲基硅酯 、 叠氮基三甲基硅烷 、 Dowex 2X₈(OH^-) 、 sodium methylate 作用下， 以 二氯甲烷 为溶剂， 反应 44.0h， 生成 methyl 2-acetamido-3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  A convenient access to β-glycosides of N-acetyllactosamine

  摘要：

  Iodoacetoxylation of 3,6-di-0-acetyI-4-0-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-1,5-anhydro-2-deoxy-D-arabino-hex-1-enitol (hexa-O-acetyllactal) and the corresponding hexa-O-benzoyl derivative, gave the alpha-1,2-trans 1-O-acetyl-2-deoxy-2-iodo adducts with high stereoselectivity and good yields. These were treated with an excess of trimethylsilyl azide in the presence of trimethylsilyl trifluoromethanesulfonate affording the corresponding alpha-1,2-trans 2-deoxy-2-iodoglycosyl azides. In the presence of an alcohol, a Staudinger reaction at the anomeric azide ledin situ to an iminophosphorane which rearranged with elimination of iodine at C-2. The aziridine intermediate thus obtained reacted with a suitable alcohol to afford the corresponding lactosamine beta-glycosides. The reaction occurred with double inversion of configuration at C-1 and C-2. Deprotection of the amine functionality and further transformation into the acetamido derivatives could be achieved without isolation of the intermediates. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0008-6215(96)00263-7
• 作为产物：
  描述：

  1',2',3',6',2,3,4,6-octa-O-acetyl-β-D-lactose 在 copper(ll) sulfate pentahydrate 、 氢溴酸 、 碘 、 copper diacetate 、 溶剂黄146 、 锌 作用下， 以 二氯甲烷 、 水 为溶剂， 生成 1,3,6-tri-O-acetyl-4-O-(2',3',4',6'-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-2-iodo-α-D-manno-pyranose
  参考文献：
  名称：

  通过Lafont中间体从乳糖轻松合成唾液酸化寡聚乳糖胺聚糖

  摘要：

  先前已证明，从乳糖容易获得的2-氨基碘化碘化乳糖胺糖苷（Lafont中间体）不适合寡糖合成的衍生化作用，但现已成功地通过水杨醛亚胺转化为适当保护的乳糖胺结构单元（13-16）用于糖基化。标题策略使我们能够快速合成Neu5Ac-α-2,3LacNAc-β-1,3LacNAc五糖和Neu5Ac-α-2,3LacNAc-β-1,3LacNAc-β-1,3LacNAc七糖。此外，该策略已被采用为其它的2-氨基糖的合成（例如，23-27），其提供对2-氨基糖积木制备一种有用的方法。

  DOI：

  10.1039/c4sc01013b

文献信息

• Synthesis of Benzaldehyde-Functionalized Glycans: A Novel Approach Towards Glyco-SAMs as a Tool for Surface Plasmon Resonance Studies
  作者：Sebastian Kopitzki、Knud J. Jensen、Joachim Thiem

  DOI：10.1002/chem.200902693

  日期：——

  In recent years the interest in tools for investigating carbohydrate–protein (CPI) and carbohydrate‐carbohydrate interactions (CCI) has increased significantly. For the investigation of CPI and CCI, several techniques employing different linking methods are available. Surface plasmon resonance (SPR) imaging is a most appropriate tool for analyzing the formation of self‐assembled monolayers (SAM) of

  近年来，人们对研究碳水化合物-蛋白质（CPI）和碳水化合物-碳水化合物相互作用（CCI）的工具的兴趣大大增加。为了调查CPI和CCI，可以使用几种采用不同链接方法的技术。表面等离振子共振（SPR）成像是分析碳水化合物衍生物可模仿糖萼的自组装单分子膜（SAM）形成的最合适工具。与先前用于分析CPI和CCI的SPR成像方法相反，本文报道的新颖方法可轻松，快速地合成接头间隔子和碳水化合物衍生物，并通过控制配体的数量和方向来增强结合作用。为了通过还原胺化固定在具有生物排斥性的氨基官能化SPR芯片上，已通过包括烯烃复分解在内的几个简便步骤合成了多种醛官能化的聚糖结构（葡萄糖，半乳糖，甘露糖，葡糖胺，纤维二糖，乳糖和乳糖胺）。提出了针对凝集素伴刀豆球蛋白A的有效固定方法和首次结合研究。
• Copper mediated iodoacetoxylation and glycosylation: effective and convenient approaches for the stereoselective synthesis of 2-deoxy-2-iodo glycosides
  作者：Suresh Kumar Battina、Sudhir Kashyap

  DOI：10.1016/j.tetlet.2016.01.035

  日期：2016.2

  Copper(II) triflate catalyzed stereoselective glycosylation of 2-iodo-glycosyl acetate donor is reported. Anomeric activation of 2-deoxy-1-O-acetyl sugar employing Cu(OTf)2 found to be an attractive as well effective alternative reagent to the most frequently used triflic acid (TfOH) source such as TMSOTf or TBSOTf. Scope of the reaction was explored for various aglycones. This protocol involves simple

  报道了三氟甲磺酸铜（II）催化2-碘-糖基乙酸乙酸酯供体的立体选择性糖基化。发现使用Cu（OTf）2的2-脱氧-1- O-乙酰基糖的端基活化是最常用的三氟甲磺酸（TfOH）来源（如TMSOTf或TBSOTf）的诱人且有效的替代试剂。探索了各种糖苷配基的反应范围。该方案涉及简单的反应操作，采用较便宜且无毒的试剂系统，并且能够立体选择性地制备2-脱氧-2-碘-糖苷。此外，CuI / NaIO 4在环境温度下在AcOH的存在下促进了各种糖类的区域选择性碘乙酰氧基化，从而获得了2-碘-糖基乙酸酯。
• Stereoselective Synthesis of α-Linked 2-Deoxy Glycosides Enabled by Visible-Light-Mediated Reductive Deiodination
  作者：Hao Wang、Jinyi Tao、Xinpei Cai、Wei Chen、Yueqi Zhao、Yang Xu、Wang Yao、Jing Zeng、Qian Wan

  DOI：10.1002/chem.201405516

  日期：2014.12.22

  2‐Deoxy sugars and their derivatives occur abundantly in many pharmaceutically important natural products. However, the construction of specific 2‐deoxy‐glycosidic bonds remains as a challenge. Herein, we report an efficient way to prepare 2‐deoxy‐α‐glycosides by glycosylation of 2‐iodo‐glycosyl acetate and subsequent visible‐light‐mediated tin‐free reductive deiodination. We have successfully applied

  2-脱氧糖及其衍生物大量存在于许多重要的天然药物中。然而，具体的2-脱氧糖苷键的构建仍然是一个挑战。在此，我们报告了一种通过2-碘-糖基乙酸乙酸酯的糖基化和随后的可见光介导的无锡还原脱碘来制备2-脱氧-α-糖苷的有效方法。我们已成功地将糖基化后去碘化策略应用于30多种单糖，二糖，三糖，四糖和十五糖的合成，并具有出色的立体选择性和效率。该方法也已用于合成包含四个α-键的2-脱氧四糖。
• Sulfonium Salts of Iodine(I) Species as Efficient Reagents for the Regioselective Bisfunctionalisation of ­Glycals and Enol Ethers
  作者：Thurpu Raghavender Reddy、Dodla Sivanageswara Rao、Kalvacherla Babachary、Sudhir Kashyap

  DOI：10.1002/ejoc.201501183

  日期：2016.1

  A new sulfonium-salt-based iodine(I) reagent system for the vicinal functionalisation of glycals and enol ethers has been developed. The unprecedented iodine(I) complex, Me3SI(OAc)2, generated in situ from Me3SI and PhI(OAc)2, effectively promoted the one-pot iodocarboxylation using carboxylic acids, and iodoazidation using NaN3 or TMSN3 (trimethylsilyl azide). The scope and generality of the new reagent

  已经开发了一种新的基于锍盐的碘 (I) 试剂系统，用于糖类和烯醇醚的邻位功能化。由 Me3SI 和 PhI(OAc)2 原位生成的前所未有的碘 (I) 络合物 Me3SI(OAc)2，有效地促进了使用羧酸的一锅碘羧化反应，以及使用 NaN3 或 TMSN3（叠氮化三甲基甲硅烷基）的碘化叠氮化反应。探索了新试剂的范围和通用性，适用于各种底物，包括各种取代的芳香族羧酸、杂环、脂环族和脂肪族羧酸和氨基酸，以高产率 (99 %) 获得各种功能化的糖缀合物非对映选择性高达 100%。
• Synthesis of multivalent N-acetyl lactosamine modified quantum dots for the study of carbohydrate and galectin-3 interactions
  作者：Yang Yang、Xiao-Chao Xue、Xiao-Feng Jin、Li-Jun Wang、Yin-Lin Sha、Zhong-Jun Li

  DOI：10.1016/j.tet.2012.06.035

  日期：2012.9

  Ternary core/shell CdSeS/ZnS-QDs coated with N-acetyl lactosamine was prepared as a fluorescent probe to study the interactions of N-acetyl lactosamine and galectin-3. The synthesis of N-acetyl lactosamine was achieved through the 'azidoiodoglycosylation' method. The amount of ligand coated on QDs was determined by H-1 NMR and ICP-OES. The interactions between carbohydrates and galectin-3 were measured using SPR. The results revealed that the affinity of galectin-3 with di- and multivalent N-acetyl lactosamine increased 20 and 184-fold, respectively. The prepared glyco-QDs could be used as an efficient fluorescent probe to study carbohydrates and galectin-3 interactions. (C) 2012 Elsevier Ltd. All rights reserved.