苄基2-乙酰氨基-2-脱氧-3-O-(2,3,4,6-四-O-乙酰基己糖吡喃糖苷)吡喃己糖苷 | 90754-57-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 苄基2-乙酰氨基-2-脱氧-3-O-(2,3,4,6-四-O-乙酰基己糖吡喃糖苷)吡喃己糖苷
• 中文别名: [(3S,4S,5S,6R)-6-[(2S,3S,5R)-3-乙酰氨基-2-苄氧基-5-羟基-6-(羟甲基)四氢吡喃-4-基]氧代-3,4,5-三乙酰氧基-四氢吡喃-2-基]甲基乙酸酯；2-乙酰氨基-3-O-(2,3,4,6-四-O-乙酰基-Β-D-吡喃半乳糖基)-2-脱氧-Α-D-吡喃半乳糖苷
• 英文名称: benzyl O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1<*>3)-2-acetamido-2-deoxy-α-D-galactopyranoside
• 英文别名: benzyl (2,3,4,6-O-tetra-O-acetyl-β-D-galactopyranosyl)-(1-> 3)-2-acetamido-2-deoxy-α-D-galactopyranoside；benzyl O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1->3)-2-acetamido-2-deoxy-α-D-galactopyranoside；benzyl (2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1→3)-2-acetamido-2-deoxy-α-D-galactopyranoside；benzyl 2-acetamido-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-α-D-galactopyranoside；Benzyl 2-acetamido-3-O-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-2-deoxy-a-D-galactopyranoside；[(2R,3S,4S,5R,6R)-6-[(2R,3R,4R,5R,6S)-5-acetamido-3-hydroxy-2-(hydroxymethyl)-6-phenylmethoxyoxan-4-yl]oxy-3,4,5-triacetyloxyoxan-2-yl]methyl acetate
• CAS: 90754-57-7
• 化学式: C₂₉H₃₉NO₁₅
• 分子量: 641.626
• InChiKey: HWDXXTUCTSBEQC-JTLQHPAOSA-N

物化性质

• 沸点：
  770.1±60.0 °C(Predicted)
• 密度：
  1.37±0.1 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿、二氯甲烷、DMSO

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  45
• 可旋转键数：
  16
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  212
• 氢给体数：
  3
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  苄基2-乙酰氨基-2-脱氧-3-O-(2,3,4,6-四-O-乙酰基己糖吡喃糖苷)吡喃己糖苷 在 二乙胺基三氟化硫 作用下， 生成 Acetic acid (2R,3R,4S,5S,6R)-4,5-diacetoxy-6-acetoxymethyl-2-((2S,3R,4R,5R,6S)-3-acetylamino-2-benzyloxy-6-fluoromethyl-5-hydroxy-tetrahydro-pyran-4-yloxy)-tetrahydro-pyran-3-yl ester
  参考文献：
  名称：

  单脱氧氟化的粘蛋白型寡糖片段的合成。

  摘要：

  DOI：

  10.1016/0008-6215(87)80111-8
• 作为产物：
  描述：

  2-乙酰氨基-2-脱氧-D-吡喃半乳糖 在 sodium acetate 、 mercury(II) cyanide 、 溶剂黄146 、 乙酰氯 、 zinc(II) chloride 作用下， 以 硝基甲烷 、 水 、 苯 为溶剂， 生成 苄基2-乙酰氨基-2-脱氧-3-O-(2,3,4,6-四-O-乙酰基己糖吡喃糖苷)吡喃己糖苷
  参考文献：
  名称：

  Structural Analysis of a Family 101 Glycoside Hydrolase in Complex with Carbohydrates Reveals Insights into Its Mechanism

  摘要：

  O-Linked glycosylation is one of the most abundant post-translational modifications of proteins. Within the secretory pathway of higher eukaryotes, the core of these glycans is frequently an N-acetylgalactosamine residue that is alpha-linked to serine or threonine residues. Glycoside hydrolases in family 101 are presently the only known enzymes to be able to hydrolyze this glycosidic linkage. Here we determine the high-resolution structures of the catalytic domain comprising a fragment of GH101 from Streptococcus pneumoniae TIGR4, SpGH101, in the absence of carbohydrate, and in complex with reaction products, inhibitor, and substrate analogues. Upon substrate binding, a tryptophan lid (residues 724-WNW-726) closes on the substrate. The closing of this lid fully engages the substrate in the active site with Asp-764 positioned directly beneath C1 of the sugar residue bound within the -1 subsite, consistent with its proposed role as the catalytic nucleophile. In all of the bound forms of the enzyme, however, the proposed catalytic acid/base residue was found to be too distant from the glycosidic oxygen (> 4.3 angstrom) to serve directly as a general catalytic acid/base residue and thereby facilitate cleavage of the glycosidic bond. These same complexes, however, revealed a structurally conserved water molecule positioned between the catalytic acid/base and the glycosidic oxygen. On the basis of these structural observations we propose a new variation of the retaining glycoside hydrolase mechanism wherein the intervening water molecule enables a Grotthuss proton shuttle between Glu-796 and the glycosidic oxygen, permitting this residue to serve as the general acid/base catalytic residue.

  DOI：

  10.1074/jbc.m115.680470

文献信息

• Synthesis of Fluorine-Containing Core-2 Tetrasaccharides
  作者：Khushi Matta、Jie Xia、James Alderfer、Conrad Piskorz、Robert Locke

  DOI：10.1055/s-2003-40342

  日期：——

  Synthesis of core-2 branched tetrasaccharides 1-3, in which a fluorine atom was substituted at the 3 or 4-position of galactose residues is described. Glycosyl imidates 13, and 19 were prepared and used to provide novel glycosyl disaccharide donors 15 and 21, respectively. Coupling of acceptor 7 with glycosyl bromide 6 provides a disaccharide that was further converted into disaccharide acceptor 8. The coupling of acceptor 14 with donor 13, and acceptor 20 with donor 19 provided disaccharides that were converted to disaccharide donors 15 and 21, respectively. Regioselective glycosylation of acceptors 8, and 16 with donors 9, 15, and 21 provided tetrasaccharides 10, 17, and 22 respectively, which were systematically deprotected to targets 1-3.

  描述了合成核心-2分支四糖 1-3，其中在半乳糖残基的 3 位或 4 位上替代了一个氟原子。准备了糖苷亚胺 13 和 19，并用于提供新型糖苷二糖供体 15 和 21。受体 7 与糖苷溴化物 6 的偶联提供了一种二糖，进一步转化为二糖受体 8。受体 14 与供体 13 的偶联，以及受体 20 与供体 19 的偶联，分别提供了二糖，转化为二糖供体 15 和 21。使用供体 9、15 和 21 对受体 8 和 16 进行区域选择性糖苷化，分别提供四糖 10、17 和 22，随后系统性去保护为目标 1-3。
• Syntheses of fluorine-containing mucin core 2/core 6 structures using novel fluorinated glucosaminyl donors
  作者：Jun Xue、Vipin Kumar、Sirajud D. Khaja、E.V. Chandrasekaran、Robert D. Locke、Khushi L. Matta

  DOI：10.1016/j.tet.2009.07.089

  日期：2009.10

  trisaccharides modified at the C-3 or C-4 position of the pertinent glucosamine residue required for mechanistic study of glycosyltransferases and sulfotransferases involved in the biosynthesis of O-glycans are reported. Novel fluorinated glucosaminyl donors were synthesized from 2-naphthylmethyl β-d-N-acetylglucosamine (β-O-NAP-GlcNAc) via double inversion of the C-3 or C-4 configuration. A one-step β-alkylation

  报道了在O-聚糖的生物合成中涉及的糖基转移酶和磺基转移酶的机理研究所需的相关葡糖胺残基的C-3或C-4位修饰的氟化粘蛋白核心6二糖和核心2三糖的合成。通过C-3或C-4构型的两次转化，由2-萘甲基β- d - N-乙酰基葡糖胺（β- O -NAP-GlcNAc）合成了新型氟化的氨基葡萄糖基供体。首次报道了GlcNAc的一步一步β-烷基化反应，以高收率提供了β- O -NAP-GlcNAc，这是寡糖合成中基于NAP-糖苷的合成策略的基石。
• A convergent synthesis of trisaccharides with α-Neu5Ac-(2→3)-β-d-Gal-(1→4)-β-d-GlcNAc and α-Neu5Ac-(2→3)-β-d-Gal-(1→3)-α-d-GalNAc sequences
  作者：Jie Xia、James L. Alderfer、Conrad F. Piskorz、Robert D. Locke、Khushi L. Matta

  DOI：10.1016/s0008-6215(00)00080-x

  日期：2000.9

  The syntheses of three trisaccharides: alpha-Neu5Ac-(2 --> 3)-beta-D-Gal-(1 --> 4)-beta-D-GlcNAc --> OMe, alpha-Neu5Ac-(2 --> 3)-beta-D-Gal6SO3Na-(1 --> 4)-beta-D-GlcNAc --> OMe, and alpha-Neu5Ac-(2 --> 3)-beta-D-Gal-(1 --> 3)-alpha-D-GalNAc --> OBn were accomplished by using either methyl (phenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-beta-D-glycero-D-g alacto-2-nonulopyranoside)onate

  三种三糖的合成：α-Neu5Ac-（2-> 3）-β-D-Gal-（1-> 4）-β-D-GlcNAc-> OMe，α-Neu5Ac-（2- > 3）-beta-D-Gal6SO3Na-（1-> 4）-beta-D-GlcNAc-> OMe和alpha-Neu5Ac-（2-> 3）-beta-D-Gal-（1- -> 3）-α-D-GalNAc-> OBn通过使用甲基（苯基5-乙酰氨基-4,7,8,9-四-O-乙酰基-3,5-二脱氧-2-硫代- β-D-甘油-Dg乳酸-2-壬基吡喃糖苷）或甲基（苯基N-乙酰基-5-乙酰氨基-4,7,8,9-四-O-乙酰基-3,5-二脱氧-2-硫代- β-D-gl羟色-D-半乳糖-2-壬基吡喃糖苷）作为唾液酸供体。在相同的糖基化条件下，N，N-二乙酰氨基唾液酸供体似乎比其母体乙酰氨基糖更具反应性。三糖以及中间产物
• Synthetic mucin fragments. Benzyl O-(2-acetamido-2-deoxy-α-d-glucopyranosyl)-(1→3)-O-β-d-galactopyranosyl-(1→3)-O- [(2-acetamido-2-deoxy-β-d-glucopyranosyl)-(1→6)]-2-acetamido-2-deoxy-α-d-galactopyranoside and benzyl O-(2-acetamido-2-deoxy- β-d-glucopyranosyl)-(1→3)-O-β-d-galactopyranosyl-(1→3)-O-[β-d-galactopyranosyl-(1→6)]-2-acetamido-2-deoxy-α-d- galactopyranoside
  作者：Rexford L. Thomas、Saeed A. Abbas、Khushi L. Matta

  DOI：10.1016/0008-6215(88)84071-0

  日期：1988.12

  which was glycosylated with 1, followed by removal of the 4-methoxybenzyl ether group, to give benzyl 2-acetamido-2-deoxy-3,4-di-O-(2,3,4,6-tetra-O-acetyl-β- d -galactopyranosyl)-α- d -galactopyranoside (7). The disaccharide diol 5, obtained from 4, and benzyl O-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β- d -glucopyranosyl-(1→3)-O-(2,4,6-tri-O- acetyl-β- d -galactopyranosyl)-(1→3)-2-acetamido-2-deoxy-α-

  摘要在4-甲苯磺酸存在下，在N，N-二甲基甲酰胺中用4-甲氧基苯甲醛二甲基乙缩醛处理苄基2-乙酰氨基-2-脱氧-α-d-吡喃半乳糖苷，得到4,6-O-（4-甲氧基苄叉）乙缩醛，其被2,3,4,6-四-O-乙酰基-α-d-吡喃半乳糖基溴化物糖基化（1）。缩醛基的还原性开环提供了6-O-（4-甲氧基苄基）衍生物（4），将其用1糖基化，然后除去4-甲氧基苄基醚基，得到苄基2-乙酰氨基-2-脱氧-3,4-二-O-（2,3,4,6-四-O-乙酰基-β-d-吡喃半乳糖苷）-α-d-吡喃半乳糖苷（7）。由4获得的二糖二醇5和苄基O-（2-乙酰氨基-3,4,6-三-O-乙酰基-2-脱氧-β-d-吡喃葡萄糖基-（1→3）-O-（2 ，4，将6-三-O-乙酰基-β-d-吡喃半乳糖苷）-（1→3）-2-乙酰氨基-2-脱氧-α-d-吡喃半乳糖苷（11）类似地用1糖基化，得到三糖衍生物9和a四糖衍生物14。二醇11也与2-甲基-（3
• Synthetic mucin fragments: Benzyl 2-acetamido-6-O-(2-acetamido-2-deoxy-β-d-glucopyranosyl)-2-deoxy-3-O-β-d-galactopyranosyl-α-d-galactopyranoside and benzyl 2-acetamido-6-O-(2-acetamido-2-deoxy-β-d-glucopyranosyl)-3-O-[6-O-(2-acetamido-2-deoxy-β-d-glucopyranosyl)-β- d-galactopyranosyl]-2-deoxy-α-d-galactopyranoside
  作者：Conrad F. Piskorz、Saeed A. Abbas、Khushi L. Matta

  DOI：10.1016/0008-6215(84)85130-7

  日期：1984.3

  Abstract Glycosylation of benzyl 2-acetamido-4,6- O -benzylidene-2-deoxy-α- d -galactopyranoside with 2,3,4,6-tetra- O -acetyl-α- d -galactopyranosyl bromide, catalyzed by mercuric cyanide, afforded benzyl-2-acetamido-4,6- O -benzylidene-2-deoxy-3- O -(2,3,4,6-tetra- O -acetyl-β- d -galactopyranosyl)-α- d -galactopyranoside ( 3 ). O -Deacetylation of 3 gave benzyl 2-acetamido-4,6- O -benzylidene-2-deoxy-3-

  摘要汞催化的2,3,4,6-四-O-乙酰基-α-d-吡喃半乳糖基溴化物的苄基2-乙酰氨基-4,6-O-亚苄基-2-脱氧-α-d-吡喃半乳糖苷的糖基化反应氰化物，得到苄基-2-乙酰氨基-4,6-O-亚苄基-2-脱氧-3-O-（2,3,4,6-四-O-乙酰基-β-d-吡喃半乳糖基）-α-d -半乳糖吡喃糖苷（3）。3的O-脱乙酰基化生成苄基2-乙酰氨基-4,6- O-亚苄基-2-脱氧-3- O-β-d-吡喃半乳糖苷-α-d-吡喃半乳糖苷，在与苯甲醛-氯化锌络合物缩醛化后，将所得的二亚苄基乙缩醛乙酰化，得到二糖二乙酸酯（7）。在热的80％乙酸水溶液中裂解3和7的缩醛基团，分别提供了二糖四乙酸盐（4）和二乙酸盐（8）。在甲醇钠甲醇中的8进行O-脱乙酰化，得到二糖（9）。4或8与2-甲基-（3,4,6-三-O-乙酰基-1,2-二脱氧-α-d-吡喃吡喃）-[2,1-d] -2-恶唑啉的缩合，然后O-脱