methyl (7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-thiotoluyl-3,5-dideoxy-D-glycero-β-D-galacto-non-2-lopyranoside)onate | 1235555-29-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-thiotoluyl-3,5-dideoxy-D-glycero-β-D-galacto-non-2-lopyranoside)onate
• 英文别名: methyl p-tolyl 7,8,9-tri-O-acetyl-5-amino-5-N,4-O-carbonyl-3,5-dideoxy-2-thio-D-glycero-β-D-galacto-2-nonulopyranosoonate；methyl (4-methylphenyl 5-amino-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-2-thio-D-glycero-β-D-galacto-non-2-ulopyranoside)onate；methyl (3aR,4R,6R,7aS)-6-(4-methylphenyl)sulfanyl-2-oxo-4-[(1S,2R)-1,2,3-triacetyloxypropyl]-3a,4,7,7a-tetrahydro-3H-pyrano[3,4-d][1,3]oxazole-6-carboxylate
• CAS: 1235555-29-9
• 化学式: C₂₄H₂₉NO₁₁S
• 分子量: 539.56
• InChiKey: UGDPCMYFECPFOX-MRNRABQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  37
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 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 (7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-thiotoluyl-3,5-dideoxy-D-glycero-β-D-galacto-non-2-lopyranoside)onate 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 methyl (5-benzyloxyacetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosyl)onate-(2→6)-1,2-3,4-diisopropyl-α-D-galactopyranoside
  参考文献：
  名称：

  Donor‐Reactivity‐Controlled Sialylation Reactions

  摘要：

  AbstractAlthough tremendous efforts have been made for the efficient preparation of sialosides, controlling the stereochemical outcome of sialylation reaction still remains one of the most challenging tasks due to the unique chemical structure of sialic acid. We developed a new strategy to statistically analyze the stereoselectivity of sialylation reactions on six types of p‐tolyl thiosialosides in NIS/TfOH system using Relative Reactivity Value (RRV) as the indicator. Analysis of the reaction mechanism showed the formation of the relatively stable glycosyl bromide and glycosyl chloride intermediates from halide‐ and triflate‐containing promotors in the absence of an acceptor. We found that the α/β‐stereoselectivity, yields, and intermediate changes were associated with their donor reactivity. These findings enable to tailor the most suitable building blocks for stereo‐controlled sialylation reactions.

  DOI：

  10.1002/ejoc.202100718
• 作为产物：
  描述：

  methyl (2-p-methylphenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α/β-D-galacto-2-thio-nonulopyranosid)onate 在 吡啶 、 甲烷磺酸 、 碳酸氢钠 作用下， 以 甲醇 、 水 、 乙腈 为溶剂， 反应 15.0h， 生成 methyl (7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-thiotoluyl-3,5-dideoxy-D-glycero-β-D-galacto-non-2-lopyranoside)onate
  参考文献：
  名称：

  Donor‐Reactivity‐Controlled Sialylation Reactions

  摘要：

  AbstractAlthough tremendous efforts have been made for the efficient preparation of sialosides, controlling the stereochemical outcome of sialylation reaction still remains one of the most challenging tasks due to the unique chemical structure of sialic acid. We developed a new strategy to statistically analyze the stereoselectivity of sialylation reactions on six types of p‐tolyl thiosialosides in NIS/TfOH system using Relative Reactivity Value (RRV) as the indicator. Analysis of the reaction mechanism showed the formation of the relatively stable glycosyl bromide and glycosyl chloride intermediates from halide‐ and triflate‐containing promotors in the absence of an acceptor. We found that the α/β‐stereoselectivity, yields, and intermediate changes were associated with their donor reactivity. These findings enable to tailor the most suitable building blocks for stereo‐controlled sialylation reactions.

  DOI：

  10.1002/ejoc.202100718

文献信息

• A Divergent Method to Prepare 5-Amino-, 5-<i>N</i>-Acetamido-, and 5-<i>N</i>-Glycolylsialosides
  作者：Thomas J. Boltje、Torben Heise、Floris P. J. T. Rutjes、Floris L. van Delft

  DOI：10.1002/ejoc.201300664

  日期：2013.8

  (non-human), or amine (cancer associated) functionality. Access to homogeneous sialosides with distinct substitution patterns is essential to determine structure–activity relationships. Herein, we report a divergent chemical approach to enable the synthesis of a library of specifically substituted sialosides by using a single sialic acid building block.

  唾液酸是涉及碳水化合物识别的生物过程的重要介质。唾液酸识别的主要决定因素是 N-5 取代基，它可以是 N-乙酰基（人）、N-羟乙酰（非人）或胺（癌症相关）功能。获得具有不同取代模式的均质唾液酸对于确定结构-活性关系至关重要。在此，我们报告了一种不同的化学方法，可以通过使用单个唾液酸构建块来合成特定取代的唾液酸苷库。
• 5-<i>N</i>,4-<i>O</i>-Carbonyl-7,8,9-tri-<i>O</i>-chloroacetyl-Protected Sialyl Donor for the Stereoselective Synthesis of α-(2→9)-Tetrasialic Acid
  作者：Chang-Ching Lin、Nai-Pin Lin、L. Sk Sahabuddin、Vijaya Raghava Reddy、Li-De Huang、Kuo Chu Hwang、Chun-Cheng Lin

  DOI：10.1021/jo100824s

  日期：2010.8.6

  An efficient stereoselective synthesis of α-(2→9)-tetrasialic acid was achieved using tri-O-chloroacetyl-derivatized sialyl donor and a triol sialyl acceptor. Both the acceptor and the donor were also protected with a cyclic 5-N-4-O-carbonyl protecting group. The donor is highly reactive and enabled α-selective sialylation with various primary, secondary, and tertiary acceptors under in situ activation

  使用三-O-氯乙酰基衍生的唾液酸供体和三醇唾液酸受体实现了α-（2→9）-四唾液酸的有效立体选择性合成。受体和供体也都被环状5- N -4- O-羰基保护基保护。供体在原位活化条件（NIS / TfOH，-78°C，乙腈/二氯甲烷）下具有高反应活性，并且能够与各种伯，仲和叔受体进行α-选择性唾液酸化。在温和的反应条件下，容易除去反式稠合的恶唑烷酮环和O-氯乙酰基保护基，以提供完全脱保护的α（2→9）-四唾液酸。
• Comparative studies on the O-sialylation with four different α/β-oriented (N-acetyl)-5-N,4-O-carbonyl-protected p-toluenethiosialosides as donors
  作者：Xiao-tai Zhang、Zhen-yuan Gu、Guo-wen Xing

  DOI：10.1016/j.carres.2014.02.006

  日期：2014.3

  Four types of 5-N,4-O-carbonyl-protected p-toluenethiosialosides were synthesized and their couplings with different acceptors were thoroughly investigated. The results indicate that the sialyl donor structure, the amount of glycosyl acceptor, and the detailed promotion conditions have great influence on the sialylation stereoselectivties and product yields. Under the (p-Tol)(2)SO/Tf2O activation conditions, the glycosylations with simple alcohols provided declined alpha-selectivities and higher yields with increasing the amounts of acceptors from 1.1 equiv to 2.0 equiv. However, the outcome of same sialylation was independent of the relative amounts of sugar alcohol acceptors. With NIS/TfOH as promoter, the alpha-selectivities of the sialylations were significantly improved compared with the cases activated by (p-Tol)(2)SO/Tf2O. In general, the difference in configuration of N-acetylated sialyl donors (D2 and D4) has little effect on the sialylation yield and stereoselectivity. In contrast, the N-deacetylated alpha/beta sialyl donors (D1 and D3) show complex sialylation profiles with different acceptors. (C) 2014 Elsevier Ltd. All rights reserved.