methyl 2β-phenylthio-4,7,8,9-tetra-O-acetyl-N,N-diacetylneuraminate | 282713-91-1

• 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: methyl 2β-phenylthio-4,7,8,9-tetra-O-acetyl-N,N-diacetylneuraminate
• 英文别名: phenyl (methyl 5-acetamido-N-acetyl-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-β-D-glycero-D-galacto-2-nonulopyranoside)onate；methyl [phenyl 4,7,8,9-tetra-O-acetyl-5-(N,N-diacetylamino)-3,5-dideoxy-2-thio-β-D-glycero-D-galacto-non-2-ulopyranoside]onate；methyl (2R,4S,5R,6R)-4-acetyloxy-5-(diacetylamino)-2-phenylsulfanyl-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 282713-91-1
• 化学式: C₂₈H₃₅NO₁₃S
• 分子量: 625.651
• InChiKey: KHUGKYDAPMVMNM-IHDDDBKGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  43
• 可旋转键数：
  16
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  203
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  methyl 2β-phenylthio-4,7,8,9-tetra-O-acetyl-N,N-diacetylneuraminate 在 4 A molecular sieve 二苯基亚砜 、 trifluoromethanesulfonic acid anhydride 、 2,4,6-三叔丁基嘧啶 作用下， 以 二氯甲烷 为溶剂， 生成 methyl 4,7,8,9-tetra-O-acetyl-5-(N-acetylacetamido)-2,3,5-trideoxy-D-glycero-D-galacto-non-2-enopyranosonate
  参考文献：
  名称：

  Efficient Glycosidation of a Phenyl Thiosialoside Donor with Diphenyl Sulfoxide and Triflic Anhydride in Dichloromethane

  摘要：

  The formation of sialic acid glycosides with a thiosialic acid derivative, diphenyl sulfoxide, and trifluoromethanesuffonic anhydride is reported. With an excess of diphenyl sulfoxide, glycal formation can be completely suppressed and excellent yields are obtained for coupling to a wide range of primary, secondary, and tertiary acceptors.

  DOI：

  10.1021/ol060030s
• 作为产物：
  描述：

  乙酸异丙烯酯 、 methyl (phenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycerol-β-D-galactonon-2-ulopyranoside)onate 在 对甲苯磺酸 作用下， 反应 16.0h， 以99%的产率得到methyl 2β-phenylthio-4,7,8,9-tetra-O-acetyl-N,N-diacetylneuraminate
  参考文献：
  名称：

  具有α-Neu5Ac-（2-> 3）-beta-D-gal-（1-> 4）-beta-D-GlcNAc和alpha-Neu5Ac-（2-> 3）-的三糖的聚合合成beta-D-gal-（1-> 3）-alpha-D-GalNAc序列。

  摘要：

  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

  DOI：

  10.1016/s0008-6215(00)00080-x

文献信息

• <i>O</i>-Sialylation with <i>N</i>-Acetyl-5-<i>N</i>,4-<i>O</i>-Carbonyl-Protected Thiosialoside Donors in Dichloromethane:  Facile and Selective Cleavage of the Oxazolidinone Ring
  作者：David Crich、Wenju Li

  DOI：10.1021/jo062431r

  日期：2007.3.1

  An N-acetyl-5-N,4-O-carbonyl-protected thiosialoside donor, the structure of which has been defined through X-ray crystallography, was prepared and tested in couplings to a wide range of acceptors. This donor gives excellent yields and α-selectivities in linking with various primary alkyl and carbohydrate acceptors under the N-iodosuccinimide and trifluoromethanesulfonic acid in situ activation method

  制备了N-乙酰基-5- N , 4 - O-羰基保护的硫唾液酸苷供体，其结构已通过 X 射线晶体学确定，并在与各种受体的偶联中进行了测试。该供体在N-碘代琥珀酰亚胺和三氟甲磺酸原位活化方法（-40 °C 在二氯甲烷中）下与各种伯烷基和碳水化合物受体连接时具有优异的产率和 α-选择性。通过与N , N-二乙酰唾液酸供体的比较研究说明了恶唑烷酮子结构对 α-唾液酸化的有利影响，该供体表现出较差的产率和 α-选择性。唾液酸化选择性与供体的异头构型无关，但与NIS/TfOH活化方法下的反应温度高度相关。与 NIS/TfOH 方法相反，Ph 2 SO/Tf 2 O 促进在二氯甲烷中产生β-选择性偶联。N-乙酰基-5- N ,4- O-羰基保护的唾液酸苷（α-和β-端基异构体）的恶唑烷酮可以通过在温和条件下用甲醇钠处理而干净地裂解，而无需去除乙酰胺。
• Total synthesis of a sialylated and sulfated oligosaccharide from O-linked glycoproteins
  作者：Jie Xia、Conrad F Piskorz、James L Alderfer、Robert D Locke、Khushi L Matta

  DOI：10.1016/s0040-4039(00)00261-6

  日期：2000.4

  The total synthesis of a sialylated and sulfated oligosaccharide 1 representative of a structure occurring in respiratory mucins has been accomplished. Our strategy depends upon the employment of 2-naphthymethyl (NAP) protection for hydroxyl functions. Choice of the well-defined sialyl donor 15 was made because of its enhanced reactivity over the parent compound 14 for glycosylation.

  已经完成了唾液酸化和硫酸化的寡糖1的全合成，该寡糖1代表了在呼吸粘蛋白中发生的结构。我们的策略取决于使用2-萘甲基（NAP）保护羟基功能。由于其相对于母体化合物14的糖基化反应增强了反应性，因此选择了明确定义的唾液酸供体15。
• One-Pot Synthesis of Sialo-Containing Glycosyl Amino Acids by Use of anN-Trichloroethoxycarbonyl-?-thiophenyl Sialoside
  作者：Hiroshi Tanaka、Masaatsu Adachi、Takashi Takahashi

  DOI：10.1002/chem.200400840

  日期：2005.1.21

  We describe an efficient synthesis of 2,6- and 2,3-sialyl T antigens linked to serine in a one-pot glycosylation. We first investigated the glycosidation of thiosialosides by varying the N-protecting group. Modification of the C-5 amino group of beta-thiosialosides into the N-9-fluorenylmethoxycarbonyl, N-2,2,2-trichloroethoxycarbonyl (N-Troc), and N-trichloroacetyl derivatives enhanced the reactivity

  我们描述了一个锅糖基化中的丝氨酸连接的2,6-和2,3-唾液酸T抗原的有效合成。我们首先通过改变N保护基研究了硫代唾液酸苷的糖基化。将β-硫代唾液酸的C-5氨基修饰为N-9-芴基甲氧基羰基，N-2,2,2-三氯乙氧基羰基（N-Troc）和N-三氯乙酰基衍生物可增强这些化合物对糖基化的反应性。最少加入3 A分子筛也可有效提高α-连接的唾液酸苷的收率。接下来，我们使用N-Troc唾液酸供体一锅合成糖基氨基酸。N-Troc衍生物可以被转化为N-乙酰基衍生物而无需氨基酸的外消旋化。分支型一锅糖基化，通过3，6-二羟基半乳糖苷与N-Troc-β-硫代苯基唾液酸的区域选择性糖基化作用引发的β-环糊精以良好的产率提供了被保护的2，6-唾液酸T抗原。由半乳糖基氟化物与N-Troc-β-硫代苯基唾液酸苷的化学选择性糖基化作用引发的线性型一锅糖基化，以优异的产率提供了受保护的2，3-唾液酸T抗原。将两个受保护
• N,N-Diacetylsialyl chloride—a novel readily accessible sialyl donor in reactions with neutral and charged nucleophiles in the absence of a promoter
  作者：Anna V. Orlova、Anna M. Shpirt、Nadezhda Y. Kulikova、Leonid O. Kononov

  DOI：10.1016/j.carres.2010.01.005

  日期：2010.4

  alpha-glycosyl phosphate, beta-glycosyl dibenzyl phosphate, alpha-glycosyl azide, alpha-phenyl thioglycoside and alpha-glycosyl xanthate in 65-82% yields and high stereoselectivity while its reactions with simple alcohols were not stereoselective. The new sialyl donor made possible the first stereoselective synthesis of sialic acid glycosyl phosphate with alpha-configuration and highly efficient synthesis

  首次制备N，N-二乙酰神经氨酸糖基氯，使其与各种亲核试剂反应，得到相应的α-糖基磷酸酯，β-糖基二苄基磷酸酯，α-糖基叠氮化物，α-苯基硫代糖苷和α-糖基黄药酸酯以65-82％的收率和高的立体选择性，而其与简单醇的反应不是立体选择性的。新的唾液酸供体使得首次立体选择性合成具有α-构型的唾液酸糖基磷酸酯和高效合成β-构型的唾液酸糖基磷酸二苄酯成为可能。
• α-Selective Sialylations at −78 °C in Nitrile Solvents with a 1-Adamantanyl Thiosialoside
  作者：David Crich、Wenju Li

  DOI：10.1021/jo7012912

  日期：2007.9.1

  [GRAPHICS]Novel 1-adamantanylthio sialosides were synthesized and coupled to acceptors under NIS/TfOH promotion conditions. These donors showed higher reactivity than the phenylthio sialosides and could be activated by NIS/TfOH in nitrile solvents at -78 degrees C to afford improved alpha-sialylations. With the N-acetyl-5-N,4-O-oxazolidinone-protected 1-adamantanylthio sialyl donor high alpha-selectivities could be achieved in the sialylations of both primary and sterically hindered secondary acceptors, including the important galactose 3-OH acceptors.