2-O-acetyl-3,4,6-tri-O-benzyl-α-D-galactopyranose | 79218-68-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-O-acetyl-3,4,6-tri-O-benzyl-α-D-galactopyranose
• 英文别名: 2-O-acetyl-3,4,6-tri-O-benzyl-D-galactopyranose；[(3R,4S,5S,6R)-2-hydroxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl] acetate
• CAS: 79218-68-1；88988-46-9；93495-88-6；108869-76-7；127875-27-8；127875-34-7；129214-38-6；148968-88-1
• 化学式: C₂₉H₃₂O₇
• 分子量: 492.569
• InChiKey: CIYOOYKJZYSBTB-LILSDYQESA-N

物化性质

• 沸点：
  614.6±55.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-O-acetyl-3,4,6-tri-O-benzyl-α-D-galactopyranose 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 4 A molecular sieve 、 三氟化硼乙醚 、 sodium methylate 、 胍 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 58.0h， 生成 allyl 2-acetamido-2-deoxy-3-O-<3,4,6-tri-O-benzyl-2-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-galactopyranosyl>-β-D-galactopyranoside
  参考文献：
  名称：

  与肿瘤相关抗原相关的寡糖。三糖α-L-岩藻糖的糖苷丙基部分I.合成p（1 2）-β-d-Gal的- p - （1→3）-β-d-Gal的p NAC中，通过识别的肿瘤抗原的组分抗体MBr1

  摘要：

  三糖α-L-岩藻糖的合成p - （1 2）-β-d-Gal的p - （1→3）-β-d-Gal的p NAC-1-OPR（2）进行说明。所述Ñ -acetylgalactosamine 6从得到4由（三氟甲基）磺酰氧基的分子内位移从位置3到位置4其伴随的迁移（由新戊酰氧基团方案1）。半乳糖基供体9是从7到8，通过用AcOH /吡啶对原酸酯官能团进行区域选择性开放，然后用CCl 3 CN和1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）处理而获得的（流程2）。在BF 3 ·OEt 2存在下6与9的糖基化产生二糖10。的选择性脱保护10在Ô Ç（2'），然后通过糖基化与12和由得到标题三糖标准脱保护2（流程3）。初步生物学测试表明2能够以剂量依赖的方式抑制单克隆抗体MBr1与靶肿瘤细胞MCF7的结合。

  DOI：

  10.1002/hlca.19940770211
• 作为产物：
  描述：

  2,3,5-三邻苄基-1-o-(4-硝基苯甲酰基)-d-阿拉伯呋喃糖 在 水 、 溶剂黄146 作用下， 以81 %的产率得到2-O-acetyl-3,4,6-tri-O-benzyl-α-D-galactopyranose
  参考文献：
  名称：

  Enynal 衍生的铜卡宾实现催化正交糖基化

  摘要：

  在此，我们提出了一种利用地球上丰富的铜卡宾进行催化正交糖基化的方法。该方法在温和条件下操作，并采用易于获得的起始材料，包括以克级合成的台式稳定的烯醛衍生糖基供体。该反应适合多种糖基受体，包括伯醇、仲醇和叔醇。烯醛衍生的铜卡宾表现出显着的反应性和选择性，允许与不同的保护基团和立体化学模式形成糖苷键。该方法提供了对 1,2-顺式和 1,2-反式糖苷键的访问。产物的立体选择性与糖基供体的异头构型无关，其也与广泛使用的炔烃和硫代糖苷供体具有正交反应性。三糖的迭代合成进一步证明了这种正交反应性的应用。

  DOI：

  10.1002/adsc.202301207

文献信息

• 2-Methoxyethyl Group for Protection of Reducing Hydroxyl Group of Aldose
  作者：Shinkiti Koto、Naohiko Morishima、Kazuhiro Takenaka、Kumi Kanemitsu、Noriko Shimoura、Miyuki Kase、Shizuko Kojiro、Teiko Nakamura、Tomoko Kawase、Shonosuke Zen

  DOI：10.1246/bcsj.62.3549

  日期：1989.11

  A variety of benzylated 1-OH derivatives, having an acetyl or an allyl group, of D-glucose, D-galactose, D-mannose, D-xylose, L-arabinose, L-fucose, and L-rhamnose, were synthesized from the corresponding protected 2-methoxyethyl glycosides through a brief treatment with TiCl4 in dichloromethane and a subsequent hydrolysis of the intermediary 1-Cl derivatives on a silica-gel column.

  多种具有乙酰基或烯丙基的 D-葡萄糖、D-半乳糖、D-甘露糖、D-木糖、L-阿拉伯糖、L-岩藻糖和 L-鼠李糖的苄基化 1-OH 衍生物合成自通过在二氯甲烷中用 TiCl4 短暂处理并随后在硅胶柱上水解中间体 1-Cl 衍生物，得到相应保护的 2-甲氧基乙基糖苷。
• Preparation of Glycyrrhetic Acid Glycosides Having Various .BETA.(1.RAR.2)-Linked Disaccharides and Their Cytoprotective Effects on Carbon Tetrachloride-Induced Hepatic Injury.
  作者：Setsuo SAITO、Kaoru KURODA、Yasunobu HAYASHI、Yuka SASAKI、Yoichi NAGAMURA、Keiji NISHIDA、Isao ISHIGURO

  DOI：10.1248/cpb.39.2333

  日期：——

  Glycyrrhetic acid glycosides (1-7) having β(1→2)-linked disaccharides such as 2-O-β-D-glucopyranosyl-β-D-galactopyranose, 2-O-β-D-galactopyranosyl-β-D-galactopyranose, 2-O-β-D-glucuronopyranosyl-β-D-galactopyranose, 2-O-β-D-glucopyranosyl-β-D-glucuronopyranose, 2-O-β-D-galactopyranosyl-β-D-glucuronopyranose, 2-O-β-D-galactopyranosyl-β-D-glucopyranose, 2-O-β-D-glucuronopyranosyl-β-D-glucopyranose, respectively, were synthesized by stepwise construction; from glucyrrhetic acid monoglycosides to the diglycosides. The cytoprotective activities of the glycosides 1-7 and 2-O-(β-D-glucopyranosyl)-β-D-glucopyranosyl-11-oxoolean-12-en-30-oate (8) were compared with natural occurring glycyrrhizin (9). Among these glycosides 1-8, glycosides 3 and 7 having β-D-glucuronopyranose (glcUA) as the only terminal sugar component were more effective materials against hepatic injury than glycyrrhizin 9.

  通过逐步构建法分别合成了 2-O-β-D-吡喃葡萄糖基-β-D-吡喃葡萄糖、2-O-β-D-吡喃半乳糖基-β-D-吡喃葡萄糖、2-O-β-D-吡喃半乳糖基-β-D-吡喃葡萄糖、2-O-β-D-吡喃葡萄糖基-β-D-吡喃葡萄糖、2-O-β-D-吡喃葡萄糖基-β-D-吡喃葡萄糖；从葡萄糖醛酸单糖苷到二糖苷。将苷 1-7 和 2-O-(β-D-吡喃葡萄糖基)-β-D-吡喃葡萄糖基-11-氧代甘草甜素-12-烯-30-酸酯（8）的细胞保护活性与天然存在的甘草甜素（9）进行了比较。在这些苷 1-8 中，苷 3 和苷 7 以 β-D-吡喃葡萄糖（glcUA）为唯一的末端糖成分，是比甘草苷 9 更有效的抗肝损伤材料。
• Is acyl migration to the aglycon avoidable in 2-acyl assisted glycosylation reactions?
  作者：Attila Bérces、Dennis M Whitfield、Tomoo Nukada、Iwona do Santos Z.、Agnes Obuchowska、Jiri J Krepinsky

  DOI：10.1139/v04-059

  日期：2004.7.1

  This report unequivocally separates orthoester formation from acyl transfer for the first time and indicates possible routes to eliminate 2-O-acyl transfer during glycosylation reactions. Experimental evidence is shown that acyl transfer from 2-O-acyl-3,4,6-tri-O-benzyl-D-galactopyranose-derived glycosyl donors decreases in the order formyl > acetyl > pivaloyl. The 2-O-benzoyl derivatives are more variable, in some cases transferring easily, and in others not at all. Density functional theory (DFT) calculations of the structure and energetics of dioxolenium ion and related intermediates suggest that a proton transfer pathway from the nucleophile to O-2 provides an explanation for the observed trends. These DFT calculations of the proton transfer pathway support a mechanism in which a relay molecule is involved. Further DFT calculations used a constraint based on linear combinations of six bond lengths to establish the sequence of bond breaking and bond forming. The calculated anomeric carbon to former carbonyl oxygen bond that breaks during acyl transfer is the longest in the formyl case and shortest in those that exhibit little or no acyl transfer. Rotation about the aromatic to carbonyl Ph—C(=O) bond is different from the alkyl series. Analysis of this proposed TS led to the postulate that 2,6-substitution may hinder rotation even more. Thus, the 2,6-dimethylbenzoyl analogue was synthesized and it does not transfer directly or by rearrangement of its readily formed orthoester. DFT calculations suggested that 2,6-dimethoxybenzoyl should also not transfer easily. Experimentally, this proved to be the case and this new 2-O-acyl protecting group cleaves at 50 °C with a 1 mol/L solution of LiOH in methanol. Thus, a calculated transition state has led to a prototype of a protecting group that solves a major problem in oligosaccharide synthesis.Key words: glycosylation, carbohydrates, quantum chemistry, reaction mechanism, neighboring-group effects.

  这份报告首次明确区分了正酯醚的形成和酰基转移，并指出了在糖基化反应中消除2-O-酰基转移的可能途径。实验证据表明，从2-O-酰基-3,4,6-三-O-苄基-D-半乳糖苷供体中的酰基转移按照甲酰 > 乙酰 > 皮酰的顺序递减。2-O-苯甲酰衍生物更为多变，在某些情况下易于转移，而在其他情况下则不会转移。密度泛函理论（DFT）计算了二氧环离子及相关中间体的结构和能量学，表明从亲核试剂到O-2的质子转移途径解释了观察到的趋势。这些DFT计算的质子转移途径支持了一个涉及继电分子的机制。进一步的DFT计算使用基于六个键长的线性组合的约束来建立键断裂和键形成的顺序。在酰基转移过程中断裂的异常碳到前羰基氧键，在甲酰情况下是最长的，在几乎没有酰基转移的情况下是最短的。芳香环到羰基Ph-C(=O)键的旋转与烷基系列不同。对这个提出的过渡态的分析导致了这样一个假设，即2,6-取代可能会更加阻碍旋转。因此，合成了2,6-二甲基苯甲酰类似物，它不会直接转移，也不会通过其容易形成的正酯醚的重排转移。DFT计算表明，2,6-二甲氧基苯甲酰也不会轻易转移。实验上证明了这一点，这种新的2-O-酰基保护基在甲醇中与1mol/L的氢氧化锂溶液在50°C下裂解。因此，计算出的过渡态导致了一种解决寡糖合成中主要问题的保护基的原型。关键词：糖基化、碳水化合物、量子化学、反应机理、邻基效应。
• Synthesis of oligosaccharins: a chemical synthesis of propylO-β-d-galactopyranosyl-(1 → 2)-O-α-d-xylopyranosyl-(1 → 6)-O-β-d-glucopyranosyl-(1 → 4)-β-d-glucopyranoside
  作者：Arlette Wotovic、Jean-Claude Jacquinet、Pierre Sinay¨

  DOI：10.1016/0008-6215(90)80143-q

  日期：1990.9

  3-di- O -acetyl-β- d -glucopyranosyl)-β- d -glucopyranoside to give crystalline allyl O -(2- O -acetyl-3,4,6-tri- O -benzyl-β- d -galactopyranosyl)- (1 → 2)- O -(3,4-di- O -benzyl- α- d -xylopyranosyl)-(1 → 6)- O -(2,3-di- O -acetyl-β- d -glucopyranosyl)-(1 → 4)-2,3,6-tri- O -acetyl-β- d -glucopyranoside ( 23 , 50%). O -Deacetylation of 23 followed by catalytic hydrogenolysis gave the title glycoside.

  摘要在二氯甲烷存在下，烯丙基3,4-二-O-苄基-β-d-吡喃吡喃糖苷与2-O-乙酰基-3,4,6-三-O-苄基-α-d-吡喃半乳糖酰氯在二氯甲烷中缩合。三氟甲磺酸银产生烯丙基2-O-（2-O-乙酰基-3,4,6-三-O-苄基-β-d-吡喃半乳糖基）-3,4-二-O-苄基-β-d-吡喃吡喃糖苷（ 7，83％）。化合物7经五步转化为2-O-（2-O-乙酰基-3,4,6-三-O-苄基-β-d-吡喃半乳糖基）-3,4-二-O-苄基-α- d-吡喃基吡喃糖基溴化物（13），立即与烯丙基2 2,3,6-tri-O-乙酰基-4-O-（2,3-di-O-乙酰基-β-d-吡喃吡喃糖基）-β缩合-d-吡喃葡萄糖苷得到结晶烯丙基O-（2-O-乙酰基-3,4,6-三-O-苄基-β-d-吡喃半乳糖基）-（1→2）-O-（3,4-di -O-苄基-α-d-吡喃吡喃糖基）-（1→6）-O-（2,3-二-O-乙酰基-β-d-吡喃吡喃糖基）-（1→4）-2
• Insights into the Activation of Alkyne-Installed Glycosyl Donors with Dual Acidic Metal Catalysts: Reaction Pathway, Influencing Factors, and Enlightenment for Glycosylation
  作者：Chenglin Cai、Xingchun Sun、Yingle Feng、Qi Zhang、Yonghai Chai

  DOI：10.1021/acs.orglett.2c02338

  日期：2022.9.2

  The activation of alkyne-installed glycosyl donors with dual acidic metal catalysts were studied. Lewis and/or π acidity-activated pathways were observed for alkynyl carbonate-, ester-, and ether-type donors, and π acidity-promoted reaction mode afforded higher efficiency and yields. The activation mode for a certain metal catalyst is determined by the nature of catalysts itself, protecting groups

  研究了用双酸性金属催化剂活化安装有炔烃的糖基供体。对于碳酸炔基酯型、酯型和醚型供体，观察到路易斯和/或 π 酸度激活途径，并且 π 酸度促进反应模式提供了更高的效率和产率。某种金属催化剂的活化方式取决于催化剂本身的性质、糖环上的保护基团、糖的种类和苷元的结构。这一发现为我们提供了关于含炔供体糖基化的宝贵见解。