N-[(4E)-1-(己糖吡喃糖苷氧基)-3-羟基-4-十八碳烯-2-基]十八烷酰胺 | 36271-49-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 鞘脂
• 中文名称: N-[(4E)-1-(己糖吡喃糖苷氧基)-3-羟基-4-十八碳烯-2-基]十八烷酰胺
• 英文名称: C18 galactosyl(β)ceramide
• 英文别名: beta-D-galactosyl-N-octadecanoylsphingosine；N-[(E,2S,3R)-3-hydroxy-1-[(2R,3R,4S,5R,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoctadec-4-en-2-yl]octadecanamide
• CAS: 36271-49-5
• 化学式: C₄₂H₈₁NO₈
• 分子量: 728.107
• InChiKey: YMYQEDCYNANIPI-NMJNODIHSA-N

物化性质

• 熔点：
  >180°C (dec.)
• 沸点：
  857.7±65.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)
• 溶解度：
  氯仿：甲醇=1：1

计算性质

• 辛醇/水分配系数(LogP)：
  12.4
• 重原子数：
  51
• 可旋转键数：
  35
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  149
• 氢给体数：
  6
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  N-[(4E)-1-(己糖吡喃糖苷氧基)-3-羟基-4-十八碳烯-2-基]十八烷酰胺 在 二正丁基氧化锡 、 三甲基铵三氧化硫共聚物 作用下， 以 甲醇 、 四氢呋喃 为溶剂， 以89%的产率得到(2S,3R,4E)-2-octadecanamido-1-O-(3-O-sulfo-β-D-galactopyranosyl)-4-octadecene-1,3-diol sodium salt
  参考文献：
  名称：

  A Properly Protected Sphingosine Acceptor for Helferich Glycosylation

  摘要：

  提供了适当保护的神经酰胺的合成及一些糖基化的例子。该化合物适合用于糖脂的制备。它已经被用于合成α-甘露糖神经酰胺和硫酸脂，利用锚式协助来解决糖苷键的立体化学问题。

  DOI：

  10.1055/s-0029-1217956
• 作为产物：
  描述：

  糖脂 在 甲醇 、 camphor-10-sulfonic acid 、 碘 、 sodium methylate 、 silver trifluoromethanesulfonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 乙二胺 、 三苯基膦 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 9.08h， 生成 N-[(4E)-1-(己糖吡喃糖苷氧基)-3-羟基-4-十八碳烯-2-基]十八烷酰胺
  参考文献：
  名称：

  Protected Sphingosine from Phytosphingosine as an Efficient Acceptor in Glycosylation Reaction

  摘要：

  A convenient, simple, and high-yielding five-step synthesis of a sphingosine acceptor from phytosphingosine is reported, and its behavior in glycosylation reactions is described. Different synthetic paths to sphingosine acceptors using tetrachlorophthalimide as a protecting group for the sphingosine amino function and different glycosylation methods have been explored. Among the acceptors tested, the easiest accessible acceptor, unprotected on the two hydroxyl groups in positions 1 and 3, was regioselectively glycosylated on the primary position, the regioselectivity depending on the donor used.

  DOI：

  10.1021/ol403688t

文献信息

• WO2008/124729
  申请人：——

  公开号：——

  公开（公告）日：——
• CD1a-binding glycosphingolipids stimulating human autoreactive T-cells: synthesis of a family of sulfatides differing in the acyl chain moiety
  作者：Federica Compostella、Laura Franchini、Gennaro De Libero、Giovanni Palmisano、Fiamma Ronchetti、Luigi Panza

  DOI：10.1016/s0040-4020(02)01092-x

  日期：2002.10

  Native sulfatide (a mixture of 3-sulfated beta-D-galactopyranosylceramides with different fatty acids at the ceramide moiety) is an antigen presented by CD1a proteins. Herein the preparation of four sulfatides, which are constituents of the natural mixture and bear palmitic, stearic, behenic or nervonic fatty acid chains, is described. Azidosphingosine was stereoselectively synthesized through a CuCN-catalyzed allylic alkylation of a hexenitol dimesylate derived from D-xylose; beta-glycosylation of azidosphingosine, with a suitable D-galactosyl trichloroacetimidate led, after reduction of the azido, group, to the galactosylsphingosine skeleton, which was derivatized with the different fatty acids. Final regioselective 3-sulfation gave the desired sulfatides, which were tested for activation of sulfatide-specific and CD1a-restricted T-cell clones. (C) 2002 Elsevier Science Ltd. All rights reserved.
• The Synthesis and Biological Characterization of a Ceramide Library
  作者：Young-Tae Chang、Jaehwa Choi、Sheng Ding、Eva E. Prieschl、Thomas Baumruker、Jae-Mok Lee、Sung-Kee Chung、Peter G. Schultz

  DOI：10.1021/ja017576o

  日期：2002.3.1

  A facile synthesis of a combinatorial ceramide library and their activities in the NF-kappaB pathway and in apoptosis induction/prevention were demonstrated. A novel NF-kappaB activating molecule was discovered among ceramide containing beta-galactose, and the structural requirements of ceramides for apoptosis induction was elucidated.
• Quantitative Measurements of Recombinant HIV Surface Glycoprotein 120 Binding to Several Glycosphingolipids Expressed in Planar Supported Lipid Bilayers
  作者：John C. Conboy、Katherine D. McReynolds、Jacquelyn Gervay-Hague、S. Scott Saavedra

  DOI：10.1021/ja011225s

  日期：2002.2.1

  The interaction of recombinant HIV-1 surface glycoprotein gp120 (rgp120) with natural isolates of lactosylceramide (LacCer), glucosylceramide (GlcCer), and galactosylceramide (GaiCer) has been quantitatively measured under equilibrium conditions using total internal reflection fluorescence (TIRF) spectroscopy. The binding affinity (K-a) of rgp120 to these glycosphingolipids (GSLs), reconstituted at 5 mol % in supported planar lipid bilayers composed of 95 mol % POPC, is ca. 10(6) M-1 for dissolved rgp120 concentrations greater than 25 nM. In contrast, at concentrations of rgp120 between 0.2 and 15 nM, rgp120 does not bind significantly to LacCer and GlcCer, but has a high affinity for GalCer with a measured K-a value of 1.6 x 10(9) M-1. However, protein surface coverage measurements show that this strong binding process accounts for very little of the total protein adsorbed over the entire concentration range studied. At a protein concentration of ca. 20 nM, the surface coverage is only 3% of that achieved at apparent saturation (i.e., when the protein concentration is ca. 220 nM). Thus the "high affinity" binding sites comprise only a small fraction of the total number of binding sites. Several other variables were investigated, Rgp120 binding behavior at membranes doped with alpha-hydroxygalactosylceramide (alpha-GalCer) was very similar to that observed with GalCer, showing that the presence/absence of an alpha-hydroxy moiety does not significantly affect galactosylceramide recognition. Phase segregation of GalCer, which occurs when the mole fraction of this GSL in a POPC bilayer exceeds ca. 0.1, was also investigated and showed no effect on binding affinity at low rgp120 concentrations. To investigate the influence of fatty acid chain length, GSLs with monodisperse C-18 and C-24 chain lengths, both with and without an alpha-hydroxy moiety, were synthesized, and their binding affinity to rgp120 was examined. Relative to the natural isolates (which contain a mixture of chain lengths), minimal differences were observed; thus among the compounds tested, fatty acid chain length does not affect GSL recognition. The results of this work should aid efforts to design anti-HIV-1 agents based on membrane-tethered, carbohydrate-based receptors for rgp120.
• Liquid secondary ionization, tandem and matrix-assisted laser desorption/ionization time-of-flight mass spectrometric characterization of glycosphingolipid derivatives
  作者：Hélène Perreault、Catherine E. Costello

  DOI：10.1002/oms.1210291205

  日期：1994.12

  AbstractPermethylated, peracetylated and perbenzoylated derivatives of glycosphingolipids (GSLs) were prepared to compare their liquid secondary ionization mass spectrometric (LSIMS) and collision‐induced dissociation tandem mass spectrometric (CID/MS/MS) fragmentation patterns and also to determine sensitivity improvement in LSIMS and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOFMS) relative to the native species. Permethylation was carried out in the liquid phase, whereas peracetylation and perbenzoylation could be effected using either liquid (bulk)‐phase or gas‐phase procedures. Lower amounts of starting material were required for the gas‐phase derivatization (⩽ 100 pmol) compared with the bulk phase (⩽1 nmol), because the former method permits more efficient sample handling. All three types of derivatives yielded sensitivity improvements of at least two orders of magnitude over the native species in both LSIMS and MALDI‐TOFMS. The behavior of the permethylated compounds was used as the benchmark for GSL structural information content in normal and tandem mass spectra. Fragments present in spectra of the three types of derivatives generated complementary information. Permethylated GSLs favored the formation of ions related to the ceramide moieties, whereas peracetylation enhanced the production of carbohydrate‐related ions. The LSI mass spectra of perbenzoylated GSLs contained information on both ceramide and sugar portions of the molecules. Each of the LSIMS, MS/MS and MALDI‐TOFMS techniques proved to be complementary to the others in this study; the use of all three is recommended for the generation of complete structural information.