2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glucopyranosyl trichloroacetimidate | 180714-32-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glucopyranosyl trichloroacetimidate
• 英文别名: Bn(-3)[Bn(-4)][Bn(-6)]Glc2Ac(b)-O-C(NH)CCl3；[(2S,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl] acetate
• CAS: 180714-32-3
• 化学式: C₃₁H₃₂Cl₃NO₇
• 分子量: 636.957
• InChiKey: PBGJEKBBQZONHS-RQKPWJHBSA-N

物化性质

• 沸点：
  646.8±65.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  42
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  96.3
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glucopyranosyl trichloroacetimidate 在 甲醇 、 草酰氯 、 三氟甲磺酸三甲基硅酯 、 sodium methylate 、 二甲基亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  A structurally diversified linker enhances the immune response to a small carbohydrate hapten

  摘要：

  用于共价连接β-甘露二糖糖结合物的系链会影响抗白色念珠菌兔抗体的特异性。我们制备了两种糖共轭物，它们含有（1 → 2）-β-甘露二糖，通过结构一致或立体分化的间隔与鸡血清白蛋白（CSA）连接，并在小鼠和兔子的免疫试验中进行了评估。用具有结构多样化连接体的共轭疫苗进行免疫，与具有结构统一连接体的共轭疫苗相比，能诱导出更高的针对白色念珠菌细胞壁磷甘露的 IgG 滴度。这些结果表明，通过使用结构多样化的连接体，亲和力成熟和特异性抗体反应可转向对所需合蛋白的识别。

  DOI：

  10.1007/s10719-011-9331-8
• 作为产物：
  描述：

  1,2-di-O-acetyl-3,4,6-tri-O-benzyl-β-D-glucopyranose 在 乙酸肼 、 potassium carbonate 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 9.0h， 生成 2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glucopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Synthesis and Growth Inhibitory Properties of Glycosides of 1-O-Hexadecyl-2-O-methyl-sn-glycerol, Analogs of the Antitumor Ether Lipid ET-18-OCH₃ (Edelfosine)

  摘要：

  Glycosylated antitumor ether lipids (GAELs), analogs of 1-O-octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (1, ET-18-OCH3, edelfosine), were synthesized in good overall yields by glycosylation of 1-O-alkyl-2-O-methyl-sn-glycerol and tested for in vitro antineoplastic activity against a variety of murine and human tumor cell lines. Stereospecific glycosylation was achieved by the use of 2-O-acetyl-3,4,6-tri-O-benzylglucopyranosyl and -mannopyranosyl trichloroacetimidates as donors, with trimethylsilyl trifluoromethanesulfonate as catalyst in the presence of molecular sieves at -78 degrees C. The GAELs differ from 1 in having the sn-3-phosphocholine residue replaced by one of the following monosaccharide residues: beta- and alpha-2-deoxy-D-arabino-hexopyranosyl, alpha-D-mannopyranosyl, 2-O-methyl-beta-D-glucopyranosyl, and 2-O-methyl-alpha-D-mannopyranosyl. 1-O-Hexadecyl-2-O-methyl-3-O-(2'-deoxy-beta-D-arabino-hexopyranosyl)-sn-glycerol (2) was more effective than 1 in inhibiting the growth of MCF-7 (human breast cancer) and its adriamycin-resistant form MCF-7/adriamycin, and murine Lewis lung cancer. cells. 2-Deoxy-beta-D-arabino-hexopyranoside 2 was also an effective growth inhibitor of two drug-resistant leukemic cell lines, P388/Adr and L1210/vmdr.

  DOI：

  10.1021/jm960164j

文献信息

• <scp>Togni‐II</scp> Reagent Mediated Selective Hydrotrifluoromethylation and Hydrothiolation of Alkenes ^†
  作者：Shuang Teng、Lingkui Meng、Bingbing Xu、Guangsheng Tu、Peng Wu、Zhiwen Liao、Yulin Tan、Jian Guo、Jing Zeng、Qian Wan

  DOI：10.1002/cjoc.202100464

  日期：2021.12

  reactions of Togni-II reagent and thiols, a thiol-tuned selective functionalization of unactivated olefins was disclosed. In combination with aryl thiols, stoichiometric amount of Togni-II reagent prompted a hydrotrifluoromethylation of alkenes, in which, aryl thiols played as reductant and hydrogen source; while by utilization of alkyl thiols, catalytic amount of Togni-II reagent initiated thiol-ene

  基于 Togni-II 试剂和硫醇的氧化还原反应，公开了未活化烯烃的硫醇调节的选择性官能化。与芳基硫醇结合，化学计量的Togni-II试剂促进烯烃的氢三氟甲基化，其中芳基硫醇作为还原剂和氢源；而通过利用烷基硫醇，催化量的Togni-II试剂引发硫醇-烯和硫醇-炔反应。报告的应用程序的特点是它们的操作简单和广泛的官能团耐受性。
• Synthetic β-1,2-Mannosyloxymannitol Glycolipid from the Fungus <i>Malassezia pachydermatis</i> Signals through Human Mincle
  作者：Phillip L. van der Peet、Christian Gunawan、Miyuki Watanabe、Sho Yamasaki、Spencer J. Williams

  DOI：10.1021/acs.joc.9b00544

  日期：2019.6.7

  2-mannosyloxymannitol glycolipid from Malassezia pachydermatis44-2, which was reported to signal through the murine Mincle receptor. Assembly of 44-2 was achieved through a highly convergent route that exploits symmetry elements inherent within this molecule and delineation of conditions that maintain the delicate l-mannitol triester-triol array. We show that 44-2 is a potent agonist of human Mincle signaling and constitutes

  Mincle是先天免疫系统的C型凝集素受体，具有通过脂类代谢产物感测病原体和共生能力的能力。尽管已经发现越来越多的细菌糖脂可以通过人Mincle发出信号，但尚无真菌代谢物可以通过人形式的该受体发出信号。我们报告了一个复杂的β-1,2-甘露糖基甘露糖醇糖脂从马拉色霉44-2的总合成，据报道可通过鼠Mincle受体发出信号。44-2的组装是通过高度收敛的途径实现的，该途径利用了该分子中固有的对称元素，并描绘了维持精致的1-甘露醇三酯三醇阵列的条件。我们证明44-2是人类Mincle信号传导的强效激动剂，并构成了首个​​可通过人类Mincle受体发出信号的真菌代谢产物，为抗真菌免疫力提供了新见解。
• D-Glucosylated Derivatives of Isofagomine and Noeuromycin and Their Potential as Inhibitors of β-Glycoside Hydrolases
  作者：Peter J. Meloncelli、Tracey M. Gloster、Victoria A. Money、Chris A. Tarling、Gideon J. Davies、Stephen G. Withers、Robert V. Stick

  DOI：10.1071/ch07188

  日期：——

  While isofagomine and noeuromycin have previously been demonstrated to be effective inhibitors of a range of exo-acting glycosidases, they are usually only very weak inhibitors of endo-glycosidases. However, the disaccharide-like 3- and 4-O-β-d-glucopyranosylisofagomines have proven to be strong inhibitors of these endo-acting enzymes that utilize multiple sub-sites. In an attempt to emulate these successes, we have prepared 3- and 4-O-β-d-glucopyranosylnoeuromycin, the former by a selective glycosylation (at O2) of benzyl 4-C-cyano-4-deoxy-α-d-arabinoside (also leading to another synthesis of 3-O-β-d-glucopyranosylisofagomine), the latter by a non-selective glycosylation of benzyl 4-O-allyl-β-l-xyloside with subsequent introduction of the required nitrile group (also leading to another synthesis of 4-O-β-d-glucopyranosylisofagomine). 3-O-β-d-Glucopyranosylnoeuromycin was evaluated as an inhibitor of a family 26 lichenase from Clostridium thermocellum, and 4-O-β-d-glucopyranosylnoeuromycin as an inhibitor of both a family 5 endo-glucanase from Bacillus agaradhaerans and a family 10 endo-xylanase from Cellulomonas fimi. We also report X-ray structural investigations of 3- and 4-O-β-d-glucopyranosylnoeuromycin in complex with the family 26 and family 5 β-glycoside hydrolases, respectively. The two d-glucosylated noeuromycins were indeed able to harness the additional binding energy from the sub-sites of their endo-glycoside hydrolase targets, and were thus excellent inhibitors (in the nanomolar range), binding as expected in the –1 and –2 sub-sites of the enzymes.

  虽然异法哥明和新霉素以前已被证明是一系列外作用糖苷酶的有效抑制剂，但它们通常只是内作用糖苷酶的非常弱的抑制剂。然而，3-和 4-O-β-d-吡喃葡萄糖异抗淀粉样二糖已被证明是这些利用多个亚位点的内切酶的强抑制剂。为了效仿这些成功经验，我们制备了 3-和 4-O-β-d-吡喃葡萄糖基诺脲霉素，前者是通过对苄基 4-氰基-4-脱氧-α-d-阿拉伯糖苷进行选择性糖基化（在 O2 处）制备的（也导致了另一种 3-O-β-d-吡喃葡萄糖基异法哥明的合成）、后者是通过对苄基 4-O-烯丙基-β-l-木糖苷进行非选择性糖基化，然后引入所需的腈基（也可导致 4-O-β-d-glucopyranosylisofagomine 的另一种合成）。我们对 3-O-β-d-Glucopyranosylnoeuromycin 和 4-O-β-d-Glucopyranosylnoeuromycin 进行了评估，前者是热细胞梭菌（Clostridium thermocellum）26 族地衣酶的抑制剂，后者是琼脂芽孢杆菌（Bacillus agaradhaerans）5 族内切葡聚糖酶和纤维单胞菌（Cellulomonas fimi）10 族内切木聚糖酶的抑制剂。我们还报告了 3- 和 4-O-β-d-glucopyranosylnoeuromycin 分别与 26 族和 5 族 β-糖苷水解酶复合物的 X 射线结构研究。这两种 d-葡糖基化的新诺霉素确实能够利用其内糖苷水解酶目标亚位点的额外结合能，因此是极好的抑制剂（在纳摩尔范围内），如预期的那样与酶的-1 和-2 亚位点结合。
• Synthesis and Immunochemical characterization of<i>S</i>-linked Glycoconjugate Vaccines against<i>Candida albicans</i>
  作者：Xiangyang Wu、Tomasz Lipinski、Eugenia Paszkiewicz、David R. Bundle

  DOI：10.1002/chem.200800352

  日期：2008.7.18

  residues are described. Syntheses were based on an oxidation-reduction strategy to construct the O-linked beta-mannopyranoside bonds and a SN2 inversion to provide 1-thio-beta-mannopyranoside residues. Subsequently the allyl trisaccharide glycosides were subjected to photo addition with cysteine amine and coupled to tetanus toxoid and bovine serum albumin with good efficiency via an adipic acid tether

  用硫原子取代糖苷氧原子是一种有前途的技术，用于产生对内源糖苷酶水解的抵抗力增强的糖缀合物。描述了两个不同的（1-> 2）-β-甘露聚糖三糖的内部残基-S-连接的甘露吡喃糖残基的合成和抗原特性。合成基于氧化还原策略来构建O-连接的β-甘露糖吡喃糖苷键和SN2反转以提供1-硫代-β-甘露糖吡喃糖苷残基。随后，用半胱氨酸胺对烯丙基三糖苷进行光加成，并通过己二酸系链以良好的效率将其与破伤风类毒素和牛血清白蛋白偶联。
• A Bacteroidetes locus dedicated to fungal 1,6-β-glucan degradation: Unique substrate conformation drives specificity of the key endo-1,6-β-glucanase
  作者：Max J. Temple、Fiona Cuskin、Arnaud Baslé、Niall Hickey、Gaetano Speciale、Spencer J. Williams、Harry J. Gilbert、Elisabeth C. Lowe

  DOI：10.1074/jbc.m117.787606

  日期：2017.6

  available to the human gut microbiota. The Bacteroides are generalist glycan degraders, and this function is mediated largely by polysaccharide utilization loci (PULs). The genomes of several Bacteroides species contain a PUL, PUL1,6-β-glucan, that was predicted to target mixed linked plant 1,3;1,4-β-glucans. To test this hypothesis we characterized the proteins encoded by this locus in Bacteroides thetaiotaomicron

  聚糖是人体肠道菌群可利用的主要营养素。拟杆菌属是通用的聚糖降解物，该功能主要由多糖利用基因座（PUL）介导。几种拟杆菌属的基因组包含PUL，PUL1,6-β-葡聚糖，预计将其靶向混合连接的植物1,3;1,4-β-葡聚糖。为了检验该假设，我们在人肠道菌群成员细菌拟杆菌（Bacteroides thetaiotaomicron）中表征了由该基因座编码的蛋白质。我们在这里显示PUL1,6-β-葡聚糖不会协调植物多糖的降解，但靶向真菌细胞壁聚糖1,6-β-葡聚糖，这是细菌的生长底物。该基因座被1,6-β-葡聚糖上调，并编码两种酶，即表面1,6-β-葡聚糖酶BT3312和主要靶向1,6-β-葡聚糖的周质β-葡糖苷酶。由PUL1,6-β-葡聚糖编码的非催化蛋白靶向1,6-β-葡聚糖，并包含表面聚糖结合蛋白和将聚糖传递至外膜转运蛋白的SusD同源物。我们通过删除BT3312来确定1,6-β-葡聚糖内切酶在1