(2S,3R,4E)-2-azido-3-(4-methoxybenzyl)-4-octadecen-1,3-diol | 152386-92-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3R,4E)-2-azido-3-(4-methoxybenzyl)-4-octadecen-1,3-diol
• 英文别名: azidosphingosine；2-azido-3-(4-methoxybenzyloxy)octadec-4-en-1-ol；(2S,3R,4E)-2-azido-3-O-para-methoxybenzyl-4-octadecence-1-ol；(E,2S,3R)-2-azido-3-[(4-methoxyphenyl)methoxy]octadec-4-en-1-ol
• CAS: 152386-92-0
• 化学式: C₂₆H₄₃N₃O₃
• 分子量: 445.646
• InChiKey: PZTRBEIWPWOYNI-FQNWZSDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  32
• 可旋转键数：
  20
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  53
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S,3R,4E)-2-azido-3-(4-methoxybenzyl)-4-octadecen-1,3-diol 在 palladium on activated charcoal 吡啶 、 4-二甲氨基吡啶 、 sodium sulfide 、 4 A molecular sieve 、 硫酸 、 氢气 、 四丁基碘化铵 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 N,N-二异丙基乙胺 作用下， 以 乙醇 、 二氯甲烷 、 苯 为溶剂， 20.0~65.0 ℃ 、448.16 kPa 条件下， 反应 36.5h， 生成 4-deoxy-KRN7000
  参考文献：
  名称：

  Efficient Synthesis of α-Galactosyl Ceramide Analogues Using Glycosyl Iodide Donors

  摘要：

  The combination of reactive galactosyl iodide donors with electron-rich acceptor lipids provides highly stereoselective and efficient routes to a GalCer analogues. Using per-O-silylated donors, key intermediates can be obtained in a three-step, one-pot sequence providing useful constructs for analogue development.

  DOI：

  10.1021/ol050659f
• 作为产物：
  描述：

  (2S,3R,4E)-2-叠氮-4-十八碳烯-1,3-二醇 在 吡啶 、 甲醇 、 三氟化硼乙醚 、 sodium hydride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 25.0h， 生成 (2S,3R,4E)-2-azido-3-(4-methoxybenzyl)-4-octadecen-1,3-diol
  参考文献：
  名称：

  Efficient Synthesis of α-Galactosyl Ceramide Analogues Using Glycosyl Iodide Donors

  摘要：

  The combination of reactive galactosyl iodide donors with electron-rich acceptor lipids provides highly stereoselective and efficient routes to a GalCer analogues. Using per-O-silylated donors, key intermediates can be obtained in a three-step, one-pot sequence providing useful constructs for analogue development.

  DOI：

  10.1021/ol050659f

文献信息

• An enantiospecific synthesis of D-erythro-sphingosine from D-tartaric acid
  作者：Peter Somfai、Roger Olsson

  DOI：10.1016/s0040-4020(01)81834-2

  日期：1993.7

  An efficient enantiospecific synthesis of D-erythro-sphingosine (1) via azidosphingosine (2) is described, the absolute stereochemistry being derived from D-tartaric acid.

  描述了通过叠氮鞘氨醇（2）有效的对映体特异性合成D-赤型-鞘氨醇（1），绝对立体化学衍生自D-酒石酸。
• One-Pot Syntheses of Immunostimulatory Glycolipids
  作者：Matthew Schombs、Francine E. Park、Wenjun Du、Suvarn S. Kulkarni、Jacquelyn Gervay-Hague

  DOI：10.1021/jo100366v

  日期：2010.8.6

  Glycolipids containing α-linked galactosyl and glucosyl moieties have been shown to possess unique immunostimulatory activity creating a need for access to diverse and anomerically pure sources of these compounds for immunological studies. To meet this demand, glycosyl iodides were enlisted in the synthesis of these biologically relevant glycoconjugates. In the first-generation protocol, per-O-benzyl galactosyl

  含有 α 连接的半乳​​糖基和葡萄糖基部分的糖脂已被证明具有独特的免疫刺激活性，因此需要获得这些化合物的各种异头纯来源以进行免疫学研究。为了满足这一需求，糖基碘化物被用于合成这些生物相关的糖缀合物。在第一代方案中，per- O-苄基半乳糖基碘与活化的鞘氨醇受体有效偶联，但发现完全功能化的神经酰胺没有反应性。为了克服这个障碍，per- O研究了-三甲基甲硅烷基糖基碘化物，并显示其与神经酰胺和甘油酯受体进行高效偶联。与其他供体所观察到的相反，我们检测到葡萄糖基和半乳糖基碘化物的反应性几乎没有差异。三甲基甲硅烷基保护基团在激活供体进行亲核攻击方面发挥双重作用，同时提供瞬时保护：甲硅烷基在甲醇分解时很容易去除。所有反应均以完全的受体区域选择性进行，无需额外的保护基操作，并且仅形成所需的 α-异头异构体。这三步，
• A General Chemoenzymatic Strategy for the Synthesis of Glycosphingolipids
  作者：Yunpeng Liu、Liuqing Wen、Lei Li、Madhusudhan Reddy Gadi、Wanyi Guan、Kenneth Huang、Zhongying Xiao、Mohui Wei、Cheng Ma、Qing Zhang、Hai Yu、Xi Chen、Peng George Wang、Junqiang Fang

  DOI：10.1002/ejoc.201600950

  日期：2016.9

  A concise, prototypical, and stereoselective strategy for the synthesis of therapeutically and immunologically significant glycosphingolipids has been developed. This strategy provides a universal platform for glycosphingolipid synthesis by block coupling of enzymatically prepared free oligosaccharideglycans to lipids using glycosyl N-phenyltrifluoroacetimidates as efficient activated intermediates

  已经开发了一种用于合成具有治疗和免疫学意义的鞘糖脂的简洁、原型和立体选择性策略。该策略通过使用糖基 N-苯基三氟乙酰亚胺酯作为有效活化中间体，将酶促制备的游离寡糖聚糖与脂质阻断偶联，为鞘糖脂合成提供了通用平台。如此处所示，使用该方法以优异的产率获得了两种不同类型的鞘糖脂。
• A Modular Synthesis of Alkynyl-Phosphocholine Headgroups for Labeling Sphingomyelin and Phosphatidylcholine
  作者：Mahendra S. Sandbhor、Jessie A. Key、Ileana S. Strelkov、Christopher W. Cairo

  DOI：10.1021/jo901824h

  日期：2009.11.20

  A general route to phospho- and sphingolipids that incorporate an alkyne in the phosphocholine headgroup is described. The strategy preserves the ammonium functionality of the phosphocholine and call be easily modified to introduce desired functional groups at the N-acyl chain. The targets accessible with this strategy provide a bioorthogonal handle for postsynthetic introduction of fluorophores or other labeling agents with aqueous phase chemistry. We report the synthesis of sphingomyelin derivatives that incorporate a fluorophore and an alkyne. The modified sphingolipids retain activity as substrates for sphingomyelinase, making these compounds viable probes of enzymatic activity. Importantly, the strategy allows modification of the lipid across the phosphodiester, making the alkyne a potential probe of sphingomyelinase activity.
• Synthesis and biological evaluation of α-galactosylceramide (KRN7000) and isoglobotrihexosylceramide (iGb3)
  作者：Chengfeng Xia、Qingjia Yao、Jens Schümann、Emmanuel Rossy、Wenlan Chen、Lizhi Zhu、Wenpeng Zhang、Gennaro De Libero、Peng George Wang

  DOI：10.1016/j.bmcl.2006.01.040

  日期：2006.4

  Glycoceramides call activate NKT cells by binding with CD1d to produce IFN-gamma, IL-4, and other cytokines. An efficient synthetic pathway for alpha-galactosylceramide (KRN7000) was established by coupling a protected galactose donor to a properly protected ceramide. During the investigation, it was discovered that when the ceramide was protected with benzyl groups, only beta-galactosylceramide was produced from the glycosylation reaction. In contrast, the ceramide with benzoyl protecting groups produced alpha-galactosylceramide. Isoglobotrihexosylceramide (iGb3) was prepared by glycosylation of Gal alpha 1-3Gal beta 1-4Glc donor with 2-azidosphingosine in high yield. Biological assays on the synthetic KRN7000 and iGb3 were performed using human and murine iNKT cell clones or hybridomas. (C) 2006 Elsevier Ltd. All rights reserved.