methyl [2-thiophenyl 7,8,9-tri-O-acetyl-4,5-O,N-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranoside]onate | 929882-35-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl [2-thiophenyl 7,8,9-tri-O-acetyl-4,5-O,N-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranoside]onate
• 英文别名: methyl (3aR,4R,6S,7aS)-2-oxo-6-phenylsulfanyl-4-[(1S,2R)-1,2,3-triacetyloxypropyl]-3a,4,7,7a-tetrahydro-3H-pyrano[3,4-d][1,3]oxazole-6-carboxylate
• CAS: 929882-35-9
• 化学式: C₂₃H₂₇NO₁₁S
• 分子量: 525.533
• InChiKey: JQQNTEZKESNNRX-GAQSFIOXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  36
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  178
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  methyl [2-thiophenyl 7,8,9-tri-O-acetyl-4,5-O,N-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranoside]onate 在 barium dihydroxide 作用下， 以 乙醇 为溶剂， 反应 16.0h， 以95%的产率得到(2S,4S,5R,6R)-5-amino-4-hydroxy-2-phenylsulfanyl-6-[(1R,2R)-1,2,3-trihydroxypropyl]oxane-2-carboxylic acid
  参考文献：
  名称：

  Application of 4,5-O,N-oxazolidinone protected thiophenyl sialosyl donor to the synthesis of α-sialosides

  摘要：

  The synthesis of a novel oxazolidinone sialosyl donor is reported. The introduction of a trans-fused ring enhances reactivity and stereoselectivity in glycosylation reactions for the synthesis of alpha-sialosides. The oxazolidinone ring can also be removed under basic conditions to afford the deprotected amine, which can be further functionalized. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.12.061
• 作为产物：
  描述：

  在 碳酸氢钠 作用下， 以 吡啶 、 水 、 乙腈 为溶剂， 反应 19.0h， 生成 methyl [2-thiophenyl 7,8,9-tri-O-acetyl-4,5-O,N-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranoside]onate
  参考文献：
  名称：

  Application of 4,5-O,N-oxazolidinone protected thiophenyl sialosyl donor to the synthesis of α-sialosides

  摘要：

  The synthesis of a novel oxazolidinone sialosyl donor is reported. The introduction of a trans-fused ring enhances reactivity and stereoselectivity in glycosylation reactions for the synthesis of alpha-sialosides. The oxazolidinone ring can also be removed under basic conditions to afford the deprotected amine, which can be further functionalized. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.12.061

文献信息

• Solvent Effect in the Synthesis of Sialosyl α(2-6) Galactosides: Is Acetonitrile the only Choice?
  作者：Cristina De Meo、Michael Farris、Nathan Ginder、Bonnie Gulley、Uvege Priyadarshani、Matthew Woods

  DOI：10.1002/ejoc.200800278

  日期：2008.7

  In spite of notable achievements for the synthesis of α-sialosides that have been made in the past decades, sialylation reactions often require low temperatures (–40 to –78 °C) and the use of acetonitrile as a solvent. Herein we report that a C-5 oxazolidinone sialosyl donor gives high yields andstereoselectivities in the presence of dichloromethane and/or tetrahydrofuran at 0 °C. Surprisingly, high

  尽管过去几十年在合成 α-唾液酸苷方面取得了显著成就，但唾液酸化反应通常需要低温（–40 至 –78 °C）并使用乙腈作为溶剂。在本文中，我们报告了 C-5 恶唑烷酮唾液酸供体在二氯甲烷和/或四氢呋喃存在下在 0°C 下具有高产率和立体选择性。令人惊讶的是，即使在环境温度下，在四氢呋喃中也能获得高立体选择性和产率。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008）
• Highly Alpha-Selective Sialyl Phosphate Donors for Efficient Preparation of Natural Sialosides
  作者：Che-Hsiung Hsu、Kuo-Ching Chu、Yih-Shyan Lin、Jeng-Liang Han、Yu-Shiang Peng、Chien-Tai Ren、Chung-Yi Wu、Chi-Huey Wong

  DOI：10.1002/chem.200903035

  日期：2010.2.8

  Hubble, bubble, toil, and trouble: The use of a new sialyl phosphate donor allows the stereoselective, one‐pot multicomponent synthesis of α‐sialooligosaccharides (see scheme).

  哈勃，气泡，辛劳和麻烦：使用新的唾液酸磷酸酯供体可以立体选择性地单锅多组分合成α-唾液寡糖（参见方案）。
• C-5 Modified S-Benzoxazolyl Sialyl Donors: Towards More Efficient Selective Sialylations
  作者：Benjamin N. Harris、Payal P. Patel、Chase P. Gobble、Matthew J. Stark、Cristina De Meo

  DOI：10.1002/ejoc.201100539

  日期：2011.7

  We previously reported that the selective activation of an S-benzoxazolyl (SBox) sialyl donor over a galactosyl acceptor equipped with a thioethyl anomeric moiety can be performed in high yield but with poor stereoselectivity. To optimize this strategy, which allows the synthesis of complex carbohydrates to be shortened, a range of SBox sialyl donors modified at C-5 were synthesized and tested. In

  我们之前报道过 S-苯并恶唑基 (SBox) 唾液酸供体在配备有硫乙基异头部分的半乳糖基受体上的选择性活化可以以高产率进行，但立体选择性较差。为了优化这一策略，缩短复杂碳水化合物的合成，合成并测试了一系列在 C-5 处修饰的 SBox 唾液酸供体。特别是，SBox 离去基团和 C-4,5 的恶唑烷酮的组合​​允许在各种溶剂和不同温度下实现出色的立体控制。在二氯甲烷/四氢呋喃 (1:1) 溶剂系统中，在三氟甲磺酸铋 (III) 存在下获得了几乎完全的立体选择性。
• Synthesis of the sialylated pentasaccharide repeating unit of the capsular polysaccharide of Streptococcus group B type VI
  作者：Tapasi Manna、Anup Kumar Misra

  DOI：10.1016/j.carres.2021.108294

  日期：2021.4

  strategy has been developed for the synthesis of the sialic acid containing pentasaccharide repeating unit of the cell wall O-antigen of Streptococcus group B type VI strain involving stereoselective α-glycosylation of sialic acid thioglycoside derivative. Stereoselective glycosylation of glycosyl trichloroacetimidate derivatives and thioglycosides were carried out using perchloric acid supported over silica

  已经开发了一种有效的合成策略，用于合成含有唾液酸的五糖重复单元的链球菌B 型 VI 型菌株的细胞壁O抗原，涉及唾液酸硫糖苷衍生物的立体选择性 α-糖基化。使用负载在二氧化硅上的高氯酸 (HClO 4 –SiO 2 ) 作为固体酸催化剂，进行糖基三氯乙酰亚胺衍生物和硫代糖苷的立体选择性糖基化。已经筛选了一组唾液酸供体以获得令人满意的糖基化反应的产率和立体化学结果。
• Synthesis and Elimination of C-3-Labeled Thiosialosides
  作者：Cristina De Meo、Clare E. Wallace、Scott A. Geringer

  DOI：10.1021/ol500917k

  日期：2014.5.16

  The synthesis of C-3-labeled phenylthio sialic acid derivatives and an investigation of stereoselectivity in elimination reactions for the synthesis of 2,3-dehydro derivatives (glycals) is described. The experimental results are consistent with the existence of a conformational change and may be indicative of the intermediacy of an all-axial oxacarbenium ion.