苄基 2-乙酰氨基-2-脱氧-4,6-O-亚苄基-alpha-D-吡喃半乳糖苷 | 3554-91-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 中文名称: 苄基 2-乙酰氨基-2-脱氧-4,6-O-亚苄基-alpha-D-吡喃半乳糖苷
• 中文别名: 苄基2-乙酰氨基-4,6-O-亚苄基-2-脱氧-Α-D-吡喃半乳糖苷；苄基2-乙酰氨基-2-脱氧-4,6-O-亚苄基-alpha-D-吡喃半乳糖苷
• 英文名称: Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-galactopyranoside
• 英文别名: benzyl 2-acetamido-4,6-benzylidene-2-deoxy-α-D-galactopyranoside；Benzyl 2-acetamido-2-deoxy-4,6-O-benzylidene-a-D-galactopyranoside；N-[(4aR,6S,7R,8R,8aR)-8-hydroxy-2-phenyl-6-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]acetamide
• CAS: 3554-91-4
• 化学式: C₂₂H₂₅NO₆
• 分子量: 399.444
• InChiKey: NXGXFAKJUWEFEC-JPMMBXSKSA-N

物化性质

• 熔点：
  241-247°C
• 溶解度：
  DMSO（微量）、甲醇（微量）、吡啶（微量）

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  86.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  苄基 2-乙酰氨基-2-脱氧-4,6-O-亚苄基-alpha-D-吡喃半乳糖苷 在 4 A molecular sieve 、 水 、 三乙基硅基三氟甲磺酸酯 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 N-[(4aR,6S,7R,8R,8aR)-2-phenyl-6-phenylmethoxy-8-[(2R,3R,4S,5R,6R)-3,4,5-trihydroxy-6-(naphthalen-2-ylmethoxymethyl)oxan-2-yl]oxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]acetamide
  参考文献：
  名称：

  Selectin ligands: 2,3,4-tri-O-acetyl-6-O-(2-naphthyl)methyl (NAP) α-d-galactopyranosyl imidate as a novel glycosyl donor for the efficient total synthesis of branched mucin core 2-structure containing the NeuAcα2,3(SO3Na-6)Galβ1,3GalNAcα sequence

  摘要：

  立体选择性和区域选择性的分支黏蛋白核心2结构2的完全合成，该结构包含NeuAcα-2,3(SO3Na-6)Galβ1,3GalNAcα序列，是通过使用关键的糖基供体19实现的。

  DOI：

  10.1039/a908511d
• 作为产物：
  描述：

  2-乙酰氨基-2-脱氧-D-吡喃半乳糖 在 乙酰氯 、 zinc(II) chloride 作用下， 生成 苄基 2-乙酰氨基-2-脱氧-4,6-O-亚苄基-alpha-D-吡喃半乳糖苷
  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。
• Preparation and some biological properties of N-acetylmuramyl-alanyl-D-isoglutamine (MDP) analogues
  作者：Milan Zaoral、Jan Ježek、Jiří Rotta

  DOI：10.1135/cccc19822989

  日期：——

  The condensation of 1-α-O-benzyl-4,6-O-benzylidene-N-acetylgalactomuramic acid (I), 1-α-O-benzyl-4,6-O-benzylidene-N-acetylallomuramic acid (VIII), and 1-α-O-benzyl-4,6-O-benzylidene-N-acetylnorallomuramic acid (XI) with alanyl-D-isoglutamine benzyl ester afforded 1-α-O-benzyl-4,6-O-benzylidene-N-acetylgalactomuramyl-alanyl-D-isoglutamine benzyl ester (XII), 1-α-O-benzyl-4,6-O-benzylidene-N-acetylallomuramyl-alanyl-D-isoglutamine benzyl ester (XIII) and 1-α-O-benzyl-4,6-O-benzylidene-N-acetylnorallomuramyl-alanyl-D-isoglutamine benzyl ester (XIV). Protecting groups were removed from XII-XIV and N-acetylgalactomuramyl-alanyl-D-isoglutamine (XV), N-acetylallomuramyl-alanyl-D-isoglutamine (XVI), and N-acetylnorallomuramyl-alanyl-D-isoglutamine (XVII) were obtained. XV-XVII showed lower pyrogenic and immunoadjuvant effect than N-acetylmuramyl-alanyl-D-isoglutamine.

  1-α-O-苄基-4,6-O-苄基亚乙酰半乳糖麦鲁酸（I），1-α-O-苄基-4,6-O-苄基亚乙酰异半乳糖麦鲁酸（VIII）和1-α-O-苄基-4,6-O-苄基亚乙酰诺异半乳糖麦鲁酸（XI）与丙氨酰-D-异谷氨酰苄酯发生缩合反应，得到1-α-O-苄基-4,6-O-苄基亚乙酰半乳糖麦鲁酰丙氨酰-D-异谷氨酰苄酯（XII），1-α-O-苄基-4,6-O-苄基亚乙酰异半乳糖麦鲁酰丙氨酰-D-异谷氨酰苄酯（XIII）和1-α-O-苄基-4,6-O-苄基亚乙酰诺异半乳糖麦鲁酰丙氨酰-D-异谷氨酰苄酯（XIV）。保护基从XII-XIV中去除，得到N-乙酰半乳糖麦鲁酰丙氨酰-D-异谷氨酰（XV），N-乙酰异半乳糖麦鲁酰丙氨酰-D-异谷氨酰（XVI）和N-乙酰诺异半乳糖麦鲁酰丙氨酰-D-异谷氨酰（XVII）。XV-XVII显示出比N-乙酰半乳糖麦鲁酰丙氨酰-D-异谷氨酰更低的致热原和免疫佐剂效应。
• Synthesis of benzyl 2-acetamido-2-deoxy-3-O-β-d-fucopyranosyl-α-d-galactopyranoside and benzyl 2-acetamido-6-O-(2-acetamido-2-deoxy-β-d-glucopyranosyl)-2-deoxy-3-O-β-d-fucopyranosyl-α-d-galactopyranoside
  作者：Conrad F. Piskorz、Saeed A. Abbas、Khushi L. Matta

  DOI：10.1016/0008-6215(84)85247-7

  日期：1984.8

  Abstract Condensation of benzyl 2-acetamido-4,6- O -benzylidene-2-deoxy-α- d -galactopyranoside with 2,3,4-tri- O -acetyl-α- d -fucopyranosyl bromide in 1:1 nitromethane-benzene, in the presence of powdered mercuric cyanide, afforded benzyl 2-acetamido-4,6- O -benzylidene-2-deoxy-3- O -(2,3,4-tri- O -acetyl-β- d -fucopyranosyl)-α- d -galactopyranoside ( 3 ). Cleavage of the benzylidene group of 3 with

  摘要苄基2-乙酰氨基-4,6-O-亚苄基-2-脱氧-α-d-吡喃半乳糖苷与1,2,3,4-三-O-乙酰基-α-d-呋喃核糖基溴在1：1硝基甲烷-中的缩合反应在氰化汞粉的存在下，苯得到苄基2-乙酰氨基-4,6-O-亚苄基-2-脱氧-3-O-（2,3,4-三-O-乙酰基-β-d-呋喃核糖基）-α-d-吡喃半乳糖苷（3）。用热的60％乙酸水溶液裂解3的亚苄基，得到二醇4，其在脱乙酰基作用下提供了二糖5。二醇4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-恶唑啉在1中的缩合，2-二氯乙烷得到三糖衍生物（7）。在甲醇中用Amberlyst A-26（OH-）阴离子交换树脂将7脱乙酰化，得到标题三糖（8）。5和8的结构由13 Cn.mr确认
• Synthesis of 2-acetamido-2-deoxy-4-O-β-d-galactopyranosyl-d-galactose
  作者：Surjit S. Rana、Joseph J. Barlow、Khushi L. Matta

  DOI：10.1016/s0008-6215(00)85566-4

  日期：1980.9
• Synthesis of benzyl O-(3-O-methyl-β-d-galactopyranosyl)-(1 → 3)-2-acetamido-2-deoxy-α-d-galactopyranoside and benzyl O-(β-d-galactopyranosyl)-(1 → 3)-2-acetamido-2-deoxy-6-O-methyl-α-d-galactopyranoside as specific acceptors for sialyltransferases
  作者：Rakesh K. Jain、Conrad F. Piskorz、E.V. Chandrasekaran、Khushi L. Matta

  DOI：10.1016/0008-6215(95)00072-2

  日期：1995.7