2-methyl{3,6-di-O-acetyl-1,2-dideoxy-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-α-D-glucopyrano}[2,1-d]oxazoline | 53167-36-5

• 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
• 英文名称: 2-methyl{3,6-di-O-acetyl-1,2-dideoxy-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-α-D-glucopyrano}[2,1-d]oxazoline
• 英文别名: 4,5-dihydro-2-methyl[1,2-dideoxy-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-α-D-glucopyranoso][2,1-d]oxazole；2-methyl-{3,6-di-O-acetyl-1,2-dideoxy-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-D-glucopyrano}-[2,1-d]-oxazoline；(2S,3R,4S,5S,6R)-2-(((3aR,5R,6S,7R,7aR)-7-acetoxy-5-(acetoxymethyl)-2-methyl-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]oxazol-6-yl)oxy)-6-(acetoxymethyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate；2,3-dihydrooxazole [2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl]-(1→4)-3,4,6-tri-O-acetyl-β-D-glucopyranoside；(3aR)-7c-acetoxy-5c-acetoxymethyl-2-methyl-(3ar,7ac)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]oxazol-6t-yl tetra-O-acetyl-β-D-galactopyranoside；O³,O⁶-diacetyl-2-amino-O¹,N-ethan-1-yl-1-ylidene-O⁴-(tetra-O-acetyl-β-D-galactopyranosyl)-α-D-2-deoxy-glucopyranose；Per-acetylated N-Acetyllactosamine oxazoline；[(3aR,5R,6S,7R,7aR)-7-acetyloxy-2-methyl-6-[(2S,3R,4S,5S,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d][1,3]oxazol-5-yl]methyl acetate
• CAS: 53167-36-5
• 化学式: C₂₆H₃₅NO₁₆
• 分子量: 617.561
• InChiKey: NZWXUILGHBRKJY-GNIOKVDUSA-N

物化性质

• 沸点：
  644.1±55.0 °C(Predicted)
• 密度：
  1.49±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  43
• 可旋转键数：
  16
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  207
• 氢给体数：
  0
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  2-methyl{3,6-di-O-acetyl-1,2-dideoxy-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-α-D-glucopyrano}[2,1-d]oxazoline 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以100%的产率得到4,5-dihydro-2-methyl[1,2-dideoxy-4-O-(β-D-galactopyranosyl)-α-D-glucopyranoso][2,1-d]oxazole
  参考文献：
  名称：

  几丁质酶和-半乳糖苷酶联用延伸N-乙酰氨基葡萄糖单元的有效方法

  摘要：

  开发了一种通过两个酶促步骤合成在非还原端具有 N-乙酰氨基葡萄糖单元的寡糖的区域选择性和立体选择性合成的新策略。第一步涉及几丁质酶催化的寡糖受体的高选择性β-N-乙酰乳糖胺化，其中N-乙酰乳糖胺的4,5-二氢恶唑衍生物作为糖基供体。在碱性条件下使用几丁质酶的过渡态类似物底物允许反应仅在合成方向上进行，同时抑制产物在水性介质中的水解。几种几丁质酶突变体也在中性条件下有效地催化糖基化。第二步是在 β-半乳糖苷酶的作用下，区域选择性切割末端半乳糖单元和相邻的 N-乙酰氨基葡糖单元之间的糖苷键。这构成了以区域选择性和立体选择性方式将 N-乙酰氨基葡糖单元添加到壳寡糖和纤维寡糖衍生物的非还原端的非常有用的方法。

  DOI：

  10.1002/1522-2675(200211)85:11<3919::aid-hlca3919>3.0.co;2-p
• 作为产物：
  描述：

  (2S,3R,4S,5S,6R)-2-(((2R,3S,4R,5R)-5-acetamido-4-acetoxy-2-(acetoxymethyl)-6-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-3-yl)oxy)-6-(acetoxymethyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以74%的产率得到2-methyl{3,6-di-O-acetyl-1,2-dideoxy-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-α-D-glucopyrano}[2,1-d]oxazoline
  参考文献：
  名称：

  One-Step TEMPO-Catalyzed and Water-Mediated Stereoselective Conversion of Glycals into 2-Azido-2-deoxysugars with a PIFA–Trimethylsilyl Azide Reagent System

  摘要：

  An unprecedented water-mediated and TEMPO-catalyzed, one-step, highly regiospecific and stereoselective functionalization of glycals to 2-azido-2-deoxysugars has been developed using a PIFA-Me3SiN3 reagent system in the presence of Bu4NHSO4 as a phase-transfer catalyst. The method is metal-free, proceeds under mild reaction conditions, and tolerates a variety of protecting groups. Using this method, the synthesis of an important trisaccharide unit bound by the monoclonal anti-I Ma antibody has also been demonstrated.

  DOI：

  10.1021/acs.orglett.8b00814

文献信息

• The design and synthesis of an α-Gal trisaccharide epitope that provides a highly specific anti-Gal immune response
  作者：Kensaku Anraku、Shun Sato、Nicholas T. Jacob、Lisa M. Eubanks、Beverly A. Ellis、Kim D. Janda

  DOI：10.1039/c7ob00448f

  日期：——

  moiety were examined for their ability to elicit immune responses in KO mice. Both target epitopes were synthesized using a two-component enzymatic system using modified disaccharide substrates containing a linker moiety for coupling. While both glycoconjugate vaccines induced the required high anti-Gal IgG antibody titers, it was found that this response had exquisite specificity for the Galα(1,3)Galβ(1

  展示Galα（1,3）Gal表位的碳水化合物抗原可被人类天然存在的抗体识别。这些抗-Gal抗体最多占血清IgG的1％，并被认为是有害的，因为它们会导致超急性器官排斥。为了模拟这种情况，将α（1,3）半乳糖基转移酶敲除小鼠接种Galα（1,3）Gal表位。在我们的研究中，检查了由方酸酯部分连接的由Galα（1,3）Galβ（1,4）GlcNAc或Galα（1,3）Galβ（1,4）Glc组成的两个α-Gal三糖表位是否存在。它们在KO小鼠中引发免疫反应的能力。使用两组分酶促系统合成两个靶标表位，所述酶联体系使用含有用于偶联的接头部分的修饰的二糖底物。尽管两种糖缀合物疫苗均能诱导所需的高抗Gal IgG抗体滴度，但发现该反应对所用的Galα（1,3）Galβ（1,4）GlcNAc半抗原具有极高的特异性，而与Galα（ 1,3）Galβ（1,4）Glc半抗原。我们的发现表明，尽管同质的糖缀合物疫
• Synthesis of a useful anomeric thioacetate of an N-acetyllactosamine derivative and its application
  作者：Koji Matsuoka、Takumi Ohtawa、Hiroshi Hinou、Tetsuo Koyama、Yasuaki Esumi、Shin-Ichiro Nishimura、Ken Hatano、Daiyo Terunuma

  DOI：10.1016/s0040-4039(03)00697-x

  日期：2003.4

  of an N-acetyllactosamine derivative was efficiently synthesized in high yield from the known 2-azido glycosyl chloride using thioacetic acid as a convenient reagent. The synthesis involved not only an SN2 replacement of the chloride by a carbothiolate anion but also a reductive acetamidation of the azide group. Applications of the thioacetate for glycosidation were demonstrated to provide both O- and

  使用硫代乙酸作为方便试剂，从已知的2-叠氮基糖基氯高效高产率地合成了N-乙酰基乳糖胺衍生物的新型异头β-硫代乙酸酯。该合成不仅涉及用硫代硫酸根阴离子对氯化物进行的S N 2取代，而且涉及叠氮化物基团的还原性乙酰胺化。已证明将硫代乙酸酯用于糖苷化可以以高收率提供O-和S-糖苷。此外，两种中间体都产生了包括硫糖苷键的一类新的糖簇。
• Chemoenzymatic Synthesis of Asymmetrical Multi-Antennary<i>N</i>-Glycans to Dissect Glycan-Mediated Interactions between Human Sperm and Oocytes
  作者：Zoeisha S. Chinoy、Frédéric Friscourt、Chantelle J. Capicciotti、Philip Chiu、Geert-Jan Boons

  DOI：10.1002/chem.201800451

  日期：2018.6.4

  Complex N‐glycans of glycoproteins of the zona pellucida (ZP) of human oocytes have been implicated in the binding of spermatozoa. The termini of these unusual bi‐, tri‐, and tetra‐antennary N‐glycans consist of the tetrasaccharide sialyl‐Lewisx (SLex), which was previously identified as the minimal epitope for sperm binding. We describe here the chemoenzymatic synthesis of highly complex triantennary

  人类卵母细胞透明带（ZP）的糖蛋白的复杂N聚糖与精子的结合有关。这些异常的双触角，三触角和四触角N-聚糖的末端由四糖唾液酸化-刘易斯x（SLe x）组成，该蛋白以前被确定为精子结合的最小表位。我们在这里描述高度复杂的三触角的酶法合成Ñ -glycans从ZP衍生携带SLE X在C-2和C-2'臂部分和唾液酸-路易斯X -Lewis X（SLE X -Le X）C-6天线和两个密切相关的类似物上的残留物。检查化合物抑制人精子与ZP相互作用的能力。发现SLe x -Le x部分对于抑制活性至关重要，而其他SLe x部分发挥的作用最小。对SLe x –Le x和SLe x的进一步研究表明，扩展结构是更有效的抑制剂。此外，制备了三价SLe x –Le x和SLe x，与单价对应物相比，它们显示出更大的抑制活性。我们的研究表明，尽管SLe x可以抑制精子的结合，在复杂的N-聚糖中呈递此表位会导致抑制潜能的丧失，在这种情况下，只有SLe
• Efficient Synthesis of Spacer-linked Dimers of <i>N</i>-Acetyllactosamine Using Microvawe-assisted Pyridinium Triflate-promoted Glycosylations with Oxazoline Donors
  作者：Stefan Oscarson、Halasayam Mohan、Emiliano Gemma、Katinka Ruda

  DOI：10.1055/s-2003-40340

  日期：——

  Application of pyridinum triflate as promoter combined with microwave heating afforded an easy and efficient synthesis of spacer-linked dimers of LacNAc from the corresponding oxazoline donor. As compared to the promoter pyridinium p-toluenesulfonate the triflate salt increased the yield of dimers with more than 30%, whereas microwave heating improved the yields with a further 15%.

  使用吡啶三氟甲磺酸盐作为促进剂，并结合微波加热，可以轻松高效地合成从相应的噁唑啉供体得到的间隔链接二聚体LacNAc。与促进剂吡啶对甲苯磺酸盐相比，三氟甲磺酸盐使二聚体的产率提高了30%以上，而微波加热进一步提高了产率15%。
• 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。