3,6-di-O-benzyl-D-galactal | 173008-15-6

• 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: 3,6-di-O-benzyl-D-galactal
• 英文别名: (2R,3R,4R)-4-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-3-ol
• CAS: 173008-15-6
• 化学式: C₂₀H₂₂O₄
• 分子量: 326.392
• InChiKey: KUSSRSMLTQREOG-VAMGGRTRSA-N

物化性质

• 沸点：
  480.5±45.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,6-di-O-benzyl-D-galactal 在 四丁基氟化铵 、 二甲基二环氧乙烷 、 三氟甲烷磺酸甲酯 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 8.25h， 生成
  参考文献：
  名称：

  Synthesis of Asialo GM₁. New Insights in the Application of Sulfonamidoglycosylation in Oligosaccharide Assembly:  Subtle Proximity Effects in the Stereochemical Governance of Glycosidation

  摘要：

  The total synthesis of asialo GM(1) (1a) has been accomplished, Using related chemistry, the methyl glycoside of the asialo compound (1b) has also been synthesized. These kinds of compounds have been identified as potential ligands for bacterial and viral infection sites, A simpler structure, which hits also been identified for its infection attracting structure in the context of glycopeptides and glycolipids (methyl glycoside 2), has also been synthesized. The key common phase in the syntheses involves the sulfonamidoglycosidation reaction which is used to create a beta-linkage leading to a galNAc residue joined to the C-4 hydroxyl group of a galactose unit either as a monosaccharide (see compound 2) or as C-4' in the contest of a lactosyl moiety, During the course of these studies there was encountered an unusual "proximal hydroxyl" directing effect. Thus, when C-4 on the galactose ring of an azaglycosylating donor bears a free hydroxyl (see, for instance, compound 13), beta-glycoside formation predominates. When this hydroxyl group is blocked, the process tends in the direction of alpha-glycoside formation (see compound 32), These findings were explained as arising from a critical intramolecular hydrogen bond between the C-4 axial hydroxyl of the galactose donor and its proximal pyranosidal ring oxygen. This interaction stabilizes conformations from which beta-glycosidation predominates.

  DOI：

  10.1021/ja9724957
• 作为产物：
  描述：

  D-吡喃葡萄糖 在 高氯酸 、 氢溴酸 、 sodium methylate 、 四丁基碘化铵 、 溶剂黄146 、 三丁基氧化锡 、 锌 作用下， 以 甲醇 、 水 、 苯 为溶剂， 生成 3,6-di-O-benzyl-D-galactal
  参考文献：
  名称：

  锈普罗维登斯氏菌O34的O-多糖的三，六和七糖亚结构的全合成。

  摘要：

  描述了一种通用且有效的策略，用于合成锈锈菌O34的脂多糖的三糖，六糖和七糖亚结构。对于七糖，采用了七个不同的结构单元。该结构的特殊特征是一个α-连接的半乳​​糖胺和两个嵌入的α-岩藻糖单元，它们在3和-4位分支或在其2位进一步连接。收敛策略集中在[4 + 3]，[3 + 4]和[4 + 2 + 1]耦合上。[4 + 3]和[3 + 4]耦合策略失败，而[4 + 2 + 1]策略成功。作为单糖结构单元，使用了三氯乙酰亚胺酸酯和磷酸盐。通过桦木反应实现了完全保护的结构的整体脱保护。

  DOI：

  10.1002/chem.202000496

文献信息

• Tin-Mediated Regioselective Benzylation and Allylation of Polyols: Applicability of a Catalytic Approach Under Solvent-Free Conditions
  作者：Maddalena Giordano、Alfonso Iadonisi

  DOI：10.1021/jo402399n

  日期：2014.1.3

  The first catalytic version of the stannylene-mediated benzylation and allylation of polyols is reported. The methodology is based on a simple solvent-free protocol that significantly advances, in terms of both experimental ease and synthetic scope, the applicability of tin-promoted selective protections. The described approach is indeed endowed with a very large number of advantages over routine protocols:

  报道了由亚苯乙烯介导的多元醇的苄基化和烯丙基化的第一个催化形式。该方法基于简单的无溶剂方案，在实验简便性和合成范围方面，都大大提高了锡促进的选择性保护的适用性。与常规方案相比，所描述的方法确实具有许多优点：使用低催化负载量的廉价Bu 2SnO是避免使用溶剂的一步法工艺，是在空气中进行反应的最低要求的实验程序，缩短了反应时间，简化了后处理工艺，目标范围广，在许多情况下，收率均优于常规协议。另外，无催化溶剂的方法将亚锡烷基化学的范围扩展到了空前的应用领域，以还原糖和合成高苄基化的结构单元，而这些过程可以通过更苛刻的程序来获得。从概念的角度来看，所描述的结果表明，无溶剂条件可以帮助开发催化方法，否则该方法在溶液中无效。
• Linear Synthesis of a Protected H-Type II Pentasaccharide Using Glycosyl Phosphate Building Blocks
  作者：Kerry Routenberg Love、Rodrigo B. Andrade、Peter H. Seeberger

  DOI：10.1021/jo015987h

  日期：2001.11.1

  a variety of nitrogen protecting groups to ensure good glucosamine donor reactivity and protecting group compatibility. The challenge to differentiate C2 of the terminal galactose in the presence of other hydroxyl and amine protecting groups prompted us to introduce the 2-(azidomethyl)benzoyl group as a novel mode of protection for carbohydrate synthesis. The compatibility of this group with traditionally

  报道了利用糖基磷酸酯和糖基三氯乙酰亚氨酸酯结构单元线性合成完全受保护的H型II血型决定子五糖。设想了血型决定簇的自动固相合成，已证明糖基磷酸酯在逐步构建复杂的寡糖（例如H型II型抗原）中的效用。中央氨基葡萄糖结构单元的安装要求筛选各种氮保护基，以确保良好的氨基葡萄糖供体反应性和保护基的相容性。在存在其他羟基和胺保护基的情况下，区分末端半乳糖的C2的挑战促使我们引入2-（叠氮甲基）苯甲酰基作为碳水化合物合成的新型保护方式。检查了该基团与传统使用的保护基的相容性，以及其在糖基化中作为C2立体定向基团的用途。2-（叠氮甲基）苯甲酰基的应用以及对糖基供体的系统评价允许五糖的完成，并提供了预期普遍适用于血型决定簇的固相支持体合成的合成策略。
• Dimethyltin Dichloride Catalyzed Regioselective Alkylation of<i>cis</i>-1,2-Diols at Room Temperature
  作者：Varma Saikam、Saidulu Dara、Mahipal Yadav、Parvinder Pal Singh、Ram A. Vishwakarma

  DOI：10.1021/acs.joc.5b01898

  日期：2015.12.18

  mild and general method for the regioselective installation of benzyl, allyl, para-methoxybenzyl and naphthyl groups on cis-1,2-diols. The optimized method operates at room temperature using dimethyltin dichloride as catalyst and silver oxide as an additive. The present method works well with both sugars (such as mono- and disaccharides) and nonsugars (such as inositols, propan-1,2-diol, 1,2-cycloalkanediols

  在这里，我们已经开发出一种温和的通用方法，用于在顺式-1，2-二醇上区域选择性地安装苄基，烯丙基，对甲氧基苄基和萘基。该优化方法在室温下使用二氯化二甲基锡作为催化剂，氧化银作为添加剂进行操作。本方法对于糖类（例如单糖和二糖）和非糖类（例如肌醇，1，2-丙二醇，1,2-环烷二醇和脱水赤藓糖醇）均适用，并且还提供了相对更好的官能团相容性。
• Regioselective mono and multiple alkylation of diols and polyols catalyzed by organotin and its applications on the synthesis of value-added carbohydrate intermediates
  作者：Hengfu Xu、Bo Ren、Wei Zhao、Xiaoting Xin、Yuchao Lu、Yuxin Pei、Hai Dong、Zhichao Pei

  DOI：10.1016/j.tet.2016.04.076

  日期：2016.6

  A catalytic amount of dibutyltin dichloride was used to develop regioselective alkylation of diols and multiple alkylation of polyols. Alkyl groups, including allyl, alkynyl and long-chain alkyl groups, were successfully introduced to one or two hydroxyl groups of carbohydrate and nonsugar substrates. In most cases, excellent isolation yields were obtained. The alkynylated carbohydrates may be used

  催化量的二氯化二丁基锡用于发展二醇的区域选择性烷基化和多元醇的多重烷基化。包括烯丙基，炔基和长链烷基在内的烷基已成功引入到碳水化合物和非糖底物的一个或两个羟基上。在大多数情况下，可获得优异的分离产率。炔化的碳水化合物可用于通过点击反应以高效率合成寡糖模拟物。具有长链烷基的碳水化合物可用作表面活性剂，本研究中的实验进一步证明了这一点。
• Influence of Gb3 glycosphingolipids differing in their fatty acid chain on the phase behaviour of solid supported membranes: chemical syntheses and impact of Shiga toxin binding
  作者：Ole M. Schütte、Annika Ries、Alexander Orth、Lukas J. Patalag、Winfried Römer、Claudia Steinem、Daniel B. Werz

  DOI：10.1039/c4sc01290a

  日期：——

  The Shiga toxin B subunit (STxB), which is involved in cell membrane attachment and trafficking of Shiga holotoxin, binds specifically to the glycosphingolipid Gb3. In biological membranes, Gb3 glycosphingolipids differ in their fatty acid composition and there is strong evidence that the fatty acid alters the binding behaviour of STxB as well as the intracellular routing of the Shiga toxin/Gb3 complex. To analyse the binding of STxB to different Gb3s, we chemically synthesized saturated, unsaturated, α-hydroxylated Gb3s and a combination thereof, all based on a C24-fatty acid chain starting from monosaccharide building blocks, sphingosine and the respective fatty acids. These chemically well-defined Gb3s were inserted into solid supported phase-separated lipid bilayers composed of DOPC/sphingomyelin/cholesterol as a simple mimetic of the outer leaflet of animal cell membranes. By fluorescence- and atomic force microscopy the phase behaviour of the bilayer as well as the lateral organization of bound STxB were analysed. The fatty acid of Gb3 significantly alters the ratio between the ordered and disordered phase and induces a third intermediate phase in the presence of unsaturated Gb3. The lateral organization of STxB on the membranes varies significantly. While STxB attached to membranes with Gb3s with saturated fatty acids forms protein clusters, it is more homogeneously bound to membranes containing unsaturated Gb3s. Large interphase lipid redistribution is observed for α-hydroxylated Gb3 doped membranes. Our results clearly demonstrate that the fatty acid of Gb3 strongly influences the lateral organization of STxB on the membrane and impacts the overall membrane organization of phase-separated lipid membranes.

  志贺毒素B亚基（STxB）参与细胞膜附着和志贺毒素的转运，特异性地结合到糖神经酰胺Gb3上。在生物膜中，Gb3糖神经酰胺的脂肪酸组成不同，有强有力的证据表明脂肪酸改变STxB的结合行为以及志贺毒素/Gb3复合物的细胞内运输途径。为了分析STxB与不同Gb3的结合，我们化学合成了饱和、不饱和、α-羟基化的Gb3及其组合，所有这些都基于从单糖构建块、鞘氨醇和相应的脂肪酸开始的C24脂肪酸链。这些化学上定义明确的Gb3被插入到由DOPC/鞘磷脂/胆固醇组成的固相分离脂质双层中，作为动物细胞膜外叶的简单模拟物。通过荧光显微镜和原子力显微镜分析了双层的相行为以及STxB结合的侧向组织。Gb3的脂肪酸显著改变了有序和无序相的比例，并在存在不饱和Gb3的情况下诱导了第三种中间相。STxB在膜上的侧向组织显著变化。当STxB附着在含有饱和脂肪酸Gb3的膜上时形成蛋白质簇，它更均匀地结合到含有不饱和Gb3的膜上。观察到α-羟基化Gb3掺杂膜的大相间脂质重分布。我们的结果清楚地表明，Gb3的脂肪酸强烈影响STxB在膜上的侧向组织，并影响相分离脂质膜的整体膜组织。