methyl p-tolyl 4,7,8,9-tetra-O-acetyl-5-(N-acetylacetamido)-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosonate | 374573-38-3

• 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 p-tolyl 4,7,8,9-tetra-O-acetyl-5-(N-acetylacetamido)-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosonate
• CAS: 374573-38-3
• 化学式: C₂₉H₃₇NO₁₃S
• 分子量: 639.678
• InChiKey: YOXOLRVAKCYSNZ-MSDMEXNYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.87
• 重原子数：
  44.0
• 可旋转键数：
  11.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  178.11
• 氢给体数：
  0.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  methyl p-tolyl 4,7,8,9-tetra-O-acetyl-5-(N-acetylacetamido)-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosonate 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 作用下， 以 二氯甲烷-D2 为溶剂， 反应 0.08h， 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：

  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：

  N-acetyl-4,7,8,9-tetra-O-acetyl-2-chloro-2-deoxyneuraminic acid methyl ester 在 对甲苯磺酸 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 33.0h， 生成 methyl p-tolyl 4,7,8,9-tetra-O-acetyl-5-(N-acetylacetamido)-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosonate
  参考文献：
  名称：

  The Thioglycoside and Glycosyl Phosphite of 5-Azido Sialic Acid: Excellent Donors for theα-Glycosylation of Primary Hydroxy Groups

  摘要：

  5-Azido sialyl donors with O-acetyl protecting groups are useful α-selective glycosylation reagents, especially for primary hydroxyl groups as acceptors. This is shown with a variety of reactions using 1 as a sialyl donor. It was also possible to synthesize NeuAcα(2→9)NeuAc as a thioglycoside donor for use in subsequent glycosylations.

  DOI：

  10.1002/1521-3773(20010803)40:15<2900::aid-anie2900>3.0.co;2-4