methyl 2-acetamido-3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-β-D-glucopyranoside | 68774-39-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-acetamido-3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-β-D-glucopyranoside
• 英文别名: methyl O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1<*>4)-3,6-di-O-acetyl-2-acetamido-2-deoxy-β-D-glucopyranoside；methyl 2-acetamido-3,6-di-O-acetyl-2-deoxy-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside；methyl O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1<*>4)-2-acetamido-3,6-di-O-acetyl-2-deoxy-β-D-glucopyranoside；2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl-(1->4)-2-deoxy-2-acetamido-3,6-di-O-acetyl-β-methyl-D-glucopyranoside；β-OMe-heptaacetyl lactosaminide；Gal2Ac3Ac4Ac6Ac(b1-4)b-GlcNAc1Me3Ac6Ac；[(2R,3S,4R,5R,6R)-5-acetamido-4-acetyloxy-6-methoxy-3-[(2S,3R,4S,5S,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxyoxan-2-yl]methyl acetate
• CAS: 68774-39-0
• 化学式: C₂₇H₃₉NO₁₇
• 分子量: 649.603
• InChiKey: MQIMSINEEFVMCI-CERFIYQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.3
• 重原子数：
  45
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  224
• 氢给体数：
  1
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  methyl 2-acetamido-3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-β-D-glucopyranoside 在 Aspergillusniger lipase immobilized on epoxy sepabeads 作用下， 以 aq. phosphate buffer 、 乙腈 为溶剂， 反应 48.0h， 以42%的产率得到methyl 2,4,6-tri-O-acetyl-β-D-galactopyranosyl-(1→4)-2-deoxy-2-acetamido-3,6-di-O-acetyl-β-D-glucopyranoside
  参考文献：
  名称：

  通过固定化的黑曲霉酯酶催化的水性和非水性介质水解二糖的区域选择性脱乙酰化

  摘要：

  从黑曲霉脂肪酶（ANL）的粗商业提取物中纯化的脂肪酶馏分被选择性地固定在疏水性支持物上。酯酶活性的显着百分比保留在上清液中，该酯酶活性源自无法吸附到所用基质上的酯酶。这些残留的蛋白质被共价固定在环氧丙烯酸树脂上。在水-助溶剂系统中测试了固定化水解酶在乙酰化二糖水解中的作用。ANL-酯酶能够催化C-2位和β- O上的乙酰化β- O-甲基乳糖苷的区域选择性脱保护-甲基乳糖苷位于C-3'位置。从未被报道过的水解产物可以被认为是合成具有生物学意义的寡糖的新基础。此外，还可以在叔丁醇中进行制备性水解。这种溶剂与ANL酯酶的稳定性兼容，并且由于其绿色状态而显得是一种新颖而有前途的方法。

  DOI：

  10.1002/cctc.201300388
• 作为产物：
  描述：

  methyl O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1<*>4)-3,6-di-O-acetyl-2-azido-2-deoxy-β-D-glucopyranoside 在 palladium on activated charcoal 吡啶 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 14.0h， 生成 methyl 2-acetamido-3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Characterization of inhibitory activities and binding mode of synthetic 6′-modified methyl N-acetyl-β-lactosaminide toward rat liver CMP-d-Neu5Ac: d-galactoside-(2 → 6)-α-d-sialyltransferase

  摘要：

  6'-Deoxy (12), 6'-thio (13), and 6'-O-tetrahydropyranosyl (14) analogues of methyl N-acetyl-beta-lactosaminide (3), were synthesized from lactose. NOE experiments proved that they adopt the same conformation as that of 3. Inhibition studies using these synthetic analogues, including the disulfide dimer 15, toward (2 --> 6)-alpha-sialyltransferase (EC 2.4.99.1) revealed that the 6'-deoxy analogue 12 had remarkable inhibitory activity as the first acceptor-analogue inhibitor for this enzyme. It is noteworthy that the disulfide 15 also behaves as an inhibitor. The results indicated that chemical modification at the 6'-position of 3 did not cause much decrease in the binding affinity to the sialyltransferase. Further, a novel possibility that the acceptor and the acceptor-analogue inhibitor can bind simultaneously to the sialyltransferase was proposed based on the inhibition studies with 12 and CMP.

  DOI：

  10.1016/0008-6215(93)84251-z

文献信息

• A convenient synthesis of N-acetyllactosamine derivatives from lactal
  作者：Alexander Toepfer、Richard R. Schmidt

  DOI：10.1016/0008-6215(93)84249-6

  日期：1993.9

  O-silyl-protected lactal 1 and bis(2,2,2-trichloroethyl) azodicarboxylate (2), the dihydrooxadiazine derivative 3 was obtained in a very high yield; transesterification with benzyl alcohol furnished the corresponding derivative 4. Treatment of 3 with methanol in the presence of BF3.OEt2 afforded the methyl lactoside derivative 5 which, after transesterification with benzyl alcohol, then hydrogenolytic

  在O-甲硅烷基保护的乳酸酯1和双（2,2,2-三氯乙基）偶氮二羧酸酯（2）的热逆型杂-Diels-Alder反应中，以非常高的产率获得了二氢恶二嗪衍生物3。与苄醇进行酯交换反应得到相应的衍生物4。在BF3.OEt2存在下用甲醇处理3，得到甲基乳糖苷衍生物5，在与苄醇进行酯交换反应后，进行氢解脱苄基作用，并与阮内镍和N进行NN裂解。 -乙酰化，提供甲基O-（2,4,6-三-O-叔丁基二甲基甲硅烷基-β-D-吡喃并吡喃糖基）-（1-> 4）-2-乙酰氨基-3,6-二-O-叔酸-高产率的丁基丁基二甲基甲硅烷基-2-脱氧-β-D-吡喃葡糖苷（7）。脱甲4，然后进行O-乙酰化，用甲醇- .OEt2形成甲基糖苷，氢解脱苄基，
• Synthesis of di-, tri-, and tetra-saccharides corresponding to receptor structures recognised by Streptococcus pneumoniae
  作者：Jan Dahmén、Gösta Gnosspelius、Ann-Charlott Larsson、Thomas Lave、Ghazi Noori、Karin P»lsson、Torbjörn Frejd、Göran Magnusson

  DOI：10.1016/0008-6215(85)85219-8

  日期：1985.4

  Syntheses are described for methyl 2-acetamido-2-deoxy-4- O -β- d -galactopyranosyl-α- d -glucopyranoside, methyl 2-acetamido-2-deoxy-4- O -β- d -galactopyranosyl-β- d -glucopyranoside, methyl 3- O -(2-acetamido-2-deoxy-β- d -glucopyranosyl-β- d -galactopyranoside, methyl 3- O -(2-acetamido-2-deoxy-4- O -β- d -galactopyranosyl-β- d -glucopyranosyl)-β- d -galactopyranoside, and methyl 4- O -[3- O -(2-acetamido-2-deoxy-4-

  摘要描述了甲基2-乙酰氨基-2-脱氧-4-O-β-d-吡喃半乳糖苷-α-d-吡喃葡萄糖苷，甲基2-乙酰氨基-2-脱氧-4- O-β-d-吡喃半乳糖苷-β的合成-d-吡喃葡萄糖苷，甲基3- O-（2-乙酰氨基-2-脱氧-β-d-吡喃葡萄糖基-β-d-吡喃半乳糖苷，甲基3- O-（2-乙酰氨基-2-脱氧-4- O-β -d-吡喃半乳糖基-β-d-吡喃吡喃糖基）-β-d-吡喃半乳糖苷和甲基4-O-[3-O-（2-乙酰氨基-2-脱氧-4-O-β-d-吡喃半乳糖基-β- d-吡喃葡萄糖基）-β-d-吡喃半乳糖基]-β-d-吡喃葡糖苷。
• Regioselective Deprotection of Peracetylated Disaccharides at the Primary Position Catalyzed by Immobilized Acetyl Xylan Esterase from Bacillus pumilus
  作者：Teodora Bavaro、Marco Filice、Paolo Bonomi、Qais Abu alassal、Giovanna Speranza、Jose M. Guisan、Marco Terreni

  DOI：10.1002/ejoc.201100944

  日期：2011.11

  In this work peracetylated lactose and related compounds have been tested as advanced intermediate substrates in enzymatic deprotections catalyzed by acetyl xylan esterase (AXE) from Bacillus pumilus. In particular, we present a simple and efficient enzymatic procedure to obtain products bearing only one free primary hydroxy group in the C6′ position of the galactoside moiety of “lacto” carbohydrates

  在这项工作中，全乙酰化乳糖和相关化合物已被测试为高级中间底物，用于由来自短小芽孢杆菌的乙酰木聚糖酯酶 (AXE) 催化的酶促脱保护。特别是，我们提出了一种简单有效的酶促程序，以获得在“乳”碳水化合物的半乳糖苷部分的 C6' 位置仅带有一个游离伯羟基的产物。特别是，在 1-O-甲基乳糖胺和六乙酰乳醛的水解中取得了良好的产率（60-70%）。获得的产品作为用于合成非常重要的生物相关寡糖的高级构建模块引起了极大的兴趣。
• Chemical Modification of Lactose. XVI. : Synthesis of Lacto-N-neohexaose
  作者：TSUKASA TAKAMURA、TAKU CHIBA、SETSUZO TEJIMA

  DOI：10.1248/cpb.29.2270

  日期：——

  Reaction of 1, 6-anhydro-2, 2', 3, 4'-tetra-O-benzyl-β-lactose (1, 1 mol eq.) with the acetylated oxazoline of N-acetyllactosamine (2, 5 mol eq.) gave the derivatives of 6'-Nacetyllactosaminyllactose (3, 24.5%) and lacto-N-neohexaose (8, 53.5%). The protecting groups of 3 and 8 were removed by means of the following series of reactions to provide the corresponding tetrasaccharide (7) and hexasaccharide (12), respectively : debenzylation followed by acetylation, acetolysis, and de-O-acetylation. 13C-nuclear magnetic resonance spectral data for the 1, 6-anhydro-β-derivatives of 7 and 12 are presented.

  1, 6-脱水-2, 2', 3, 4'-四-O-苄基-β-乳糖（1, 1 mol eq.）与乙酰化 N-乙酰乳糖胺（2, 5 mol eq.）的乙酰化氧杂啉反应，产生了 6'-N-乙酰乳糖胺乳糖（3, 24.5%）和乳糖-N-新己糖（8, 53.5%）的衍生物。通过以下一系列反应，分别除去 3 和 8 的保护基团，得到相应的四糖（7）和六糖（12）：脱苄基化、乙酰化、乙酰化、脱 O-乙酰化。13C-核磁共振光谱数据用于 7 和 12 的 1, 6-脱水-β-衍生物。
• A convenient access to β-glycosides of N-acetyllactosamine
  作者：Dominique Lafont、Paul Boullanger、Francine Carvalho、Philippe Vottero

  DOI：10.1016/s0008-6215(96)00263-7

  日期：1997.1

  Iodoacetoxylation of 3,6-di-0-acetyI-4-0-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-1,5-anhydro-2-deoxy-D-arabino-hex-1-enitol (hexa-O-acetyllactal) and the corresponding hexa-O-benzoyl derivative, gave the alpha-1,2-trans 1-O-acetyl-2-deoxy-2-iodo adducts with high stereoselectivity and good yields. These were treated with an excess of trimethylsilyl azide in the presence of trimethylsilyl trifluoromethanesulfonate affording the corresponding alpha-1,2-trans 2-deoxy-2-iodoglycosyl azides. In the presence of an alcohol, a Staudinger reaction at the anomeric azide ledin situ to an iminophosphorane which rearranged with elimination of iodine at C-2. The aziridine intermediate thus obtained reacted with a suitable alcohol to afford the corresponding lactosamine beta-glycosides. The reaction occurred with double inversion of configuration at C-1 and C-2. Deprotection of the amine functionality and further transformation into the acetamido derivatives could be achieved without isolation of the intermediates. (C) 1997 Elsevier Science Ltd.