allyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,54-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosonic acid methyl ester | 73159-07-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,54-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosonic acid methyl ester
• 英文别名: Methyl (allyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosid)onate；methyl 2-allyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulosonate；methyl 2-O-α-allyl-4,7,8,9-tetra-O-acetyl-N-acetylneuraminate；methyl (2R,4S,5R,6R)-5-acetamido-4-acetyloxy-2-prop-2-enoxy-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 73159-07-6
• 化学式: C₂₃H₃₃NO₁₃
• 分子量: 531.514
• InChiKey: MDHGVFXEYFQUKV-CFPLAWGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  37
• 可旋转键数：
  17
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  179
• 氢给体数：
  1
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  allyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,54-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosonic acid methyl ester 在 sodium tetrahydroborate 、 sodium periodate 、 Amberlite IRA 400 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 5.0h， 生成 (2R,4S,5R,6R)-5-Acetylamino-2-allyloxy-4-hydroxy-6-hydroxymethyl-tetrahydro-pyran-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Synthesis of protein conjugates and analogues of N-acetylneuraminic acid

  摘要：

  N-乙酰神经酰胺酸（1）是通过改进的程序从中国燕子的唾液腺黏蛋白中制备的，该程序使用酸性树脂水解。化合物1通过新的两步程序转化为已知的乙酰氯乙酰神经酸（3）。对3进行Koenigs-Knorr糖基化，然后通过随后的还原臭氧裂解2-丙烯基α-糖苷制得关键的醛前体7和8，它们通过还原胺化与牛血清白蛋白或破伤风类毒素结合。研究了影响合并程度的因素。还合成了一系列在战略性功能上修改的N-乙酰神经酰胺酸类似物。关键词：唾液酸，N-乙酰神经酰胺酸，新糖蛋白，牛血清白蛋白，破伤风类毒素。

  DOI：

  10.1139/v90-313
• 作为产物：
  描述：

  methyl 5-acetamido-2,4,7,8,9-penta-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranosonate 在 盐酸 、 silver salicylate 、 乙酰氯 作用下， 反应 38.0h， 生成 allyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,54-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosonic acid methyl ester
  参考文献：
  名称：

  Stereoselective Synthesis of Neu5Acα(2→5)Neu5Gc:  The Building Block of Oligo/Poly(→5-O_glycolylNeu5Gcα2→) Chains in Sea Urchin Egg Cell Surface Glycoprotein

  摘要：

  The synthesis of a sialic acid dimer derivative, Neu5Acalpha(2-->5)Neu5Gc, is described. The synthetic strategy is based on the use of allyl alcohol to achieve an exclusive alpha-sialylation product. The allyloxy group is also a latent glycolic acid that provides the subsequent coupling with neuraminate with minimal protection-deprotection manipulations.

  DOI：

  10.1021/jo025988p

文献信息

• Phosphite-based sialic acid donors in the synthesis of α(2→9) oligosialic acids
  作者：Chang-Ching Lin、Avijit Kumar Adak、Jia-Cherng Horng、Chun-Cheng Lin

  DOI：10.1016/j.tet.2009.04.022

  日期：2009.6

  The combination of a phosphite donor and an anomeric thiocresol-protected acceptor, both with a TFA protecting group at C-5 of the sialic acid, provides good α-selectivity and yield in sialylation. Although the convergent synthetic strategy of using a phosphite disialo-donor and a disialo-acceptor assembles tetra-sialic acid efficiently, overcoming the low α-selectivity of α-anomer and purifying it

  亚磷酸酯供体和异头硫醇甲酚保护的受体的组合，在唾液酸的C-5处均具有TFA保护基，在唾液酸化中提供了良好的α-选择性和产率。尽管使用亚磷酸酯二唾液酸供体和二唾液酸受体的会聚合成策略有效地组装了四唾液酸，但是仍然需要克服α-端基异构体的低α-选择性并对其进行纯化。此外，将单唾液酸和二唾液酸分别缀合在载体蛋白，匙孔血蓝蛋白上。建议使用酶水解方法估算蛋白质偶联物上唾液酸的量。
• Synthesis of Novel Mimetics of CMP-Sialic Acid as the Inhibitors of Sialyltransferases
  作者：Tetsuya Kajimoto、Toru Tanaka、Machiko Ozawa、Tsuyoshi Miura、Toshiyuki Inazu、Shuichi Tsuji

  DOI：10.1055/s-2002-33518

  日期：——

  Novel mimetics of CMP-sialic acid were designed as the inhibitors of sialyltransferases. They were synthesized in a short step from a cytosine carrying β-hydroxy-α-l-amino acid based on the knowledge that nikkomycin, a peptidic derivative of an uracil carrying amino acid, shows a potent inhibitory activity toward N-acetyl-d-glucosaminyltransferases that employ UDP-N-acetyl-d-glucosamine as the donor substrate. The cytosine carrying β-hydroxyl-α-l-amino acid, a key intermediate in our synthetic strategy, was easily prepared by the l-threonine aldolase (LTA) catalyzed reaction.

  我们设计了 CMP-硅酸的新型模拟物作为硅氨酰转移酶的抑制剂。根据携带尿嘧啶的氨基酸的肽衍生物尼可霉素对使用 UDP-N- 乙酰基-d-葡糖胺作为供体底物的 N-乙酰基-d-葡糖胺转移酶具有强效抑制活性的知识，我们在短时间内从携带δ-羟基-±-l-氨基酸的胞嘧啶中合成了它们。在我们的合成策略中，胞嘧啶携带的δ-羟基-δ-±-l-氨基酸是一个关键的中间体，很容易通过 l-苏氨酸醛缩酶（LTA）催化反应制备出来。
• 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。
• A new approach to the synthesis of 5-N-acetyl-D-neuraminic acid α-ketosides
  作者：Volker Eschenfelder、Reinhard Brossmer

  DOI：10.1016/s0008-6215(00)83672-1

  日期：1980.1
• Facile Preparation of Divalent Sialoside Derivatives by Olefin Metathesis Reaction
  作者：Zhonghong Gan、René Roy

  DOI：10.1016/s0040-4020(00)00034-x

  日期：2000.3

  Olefin metathesis catalyzed by RuCl2(CHPh)(PCy3)(2) (1) has been used to synthesize homodimers of O- and S-alkenyl alpha-sialoside derivatives. The reactions afforded reasonable to good yields under mild reaction conditions. Trans-geometrical isomers were preferred in all cases. (C) 2000 Elsevier Science Ltd. All rights reserved.