Benzoic acid (E)-(R)-1-[(R)-1-(2,2-dichloro-acetylamino)-2-iodo-ethyl]-hexadec-2-enyl ester | 173067-92-0

• 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: Benzoic acid (E)-(R)-1-[(R)-1-(2,2-dichloro-acetylamino)-2-iodo-ethyl]-hexadec-2-enyl ester
• CAS: 173067-92-0
• 化学式: C₂₇H₄₀Cl₂INO₃
• 分子量: 624.43
• InChiKey: IAQCJVSPWGXQNB-MLQNYIGJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.19
• 重原子数：
  34.0
• 可旋转键数：
  19.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  55.4
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  Benzoic acid (E)-(R)-1-[(R)-1-(2,2-dichloro-acetylamino)-2-iodo-ethyl]-hexadec-2-enyl ester 在 甲醇 、 氢氧化钾 、 sodium acetate 、 potassium carbonate 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 57.0h， 生成 S-β-D-glucopyranosyl-(1<*>1)-(2R,3R,4E)-3-hydroxy-2-<8-N-(7-nitrobenz-1,3-diazol-2-oxa-4-yl)amino>octanamido-4-octadecen-1-thiol
  参考文献：
  名称：

  Synthesis of fluorescent and radioactive analogues of two lactosylceramides and glucosylceramide containing β-thioglycosidic bonds that are resistant to enzymatic degradation

  摘要：

  Condensation of 2-S-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-2-thiopseudourea hydrobromide with 2,3,6-tri-O-benzoyl-4-O-trifluoromethylsulfonyl-beta-D-galactopyranosy-(1-->1)-(2S,3R,4E)-3-O-benzoyl-2-dichloroacetamido-4-octadecan afforded S-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-(1-->4)-2,3,6-tri-O-benzoyl-4-thio-beta-D-glucopyranosyl-(1-->1)-(2S, 3R,4E)-3-O-benzoyl-2-dichloroacetamido-4 in good yield. Removal of the protecting groups, followed by selective N-acylation of the sphingosine amino group with either a fluorescent or a radioactive fatty acid, gave labeled lactosylceramide analogues in good yield. Since these products contained a beta-thioglycosidic bond between the two sugar moieties, they were totally resistant to the action of acid lysosomal glycosidases. Likewise, condensation of 2-S(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosy hydrobromide and 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl-(1-->4)-2,3,6-tri-O- acetyl-1-S-acetyl-1-thio-beta-D-glucopyranose with (2R,3R,4E)-3-O-benzoyl-2-dichloroacetamido-1-iodo-4-octadecen-3-ol in methanolic sodium acetate afforded the corresponding beta-thioglycosides 14 and 16, respectively, in good yield. These beta-thioglycosides were converted into glucosylceramide and lactosylceramide analogues following removal of the protecting groups and by subsequent selective N-acylation using either a fluorescent or radioactive fatty acid N-succinimidyl ester. Whereas the glucosylthioceramides thus obtained proved to be completely undegradable by lysosomal glucocerebrosidase, the lactosylceramides containing the beta-thioglycosidic bond between the lactose and the ceramide residues could be degraded by lysosomal GM1-beta-galactosidase to give the corresponding glucosylthioceramides. These compounds did not yield to any further enzymatic degradation.

  DOI：

  10.1016/0008-6215(95)00189-z
• 作为产物：
  描述：

  (2S,3R,4E)-3-O-benzoyl-1-O-tert-butyldiphenylsilyl-2-dichloroacetamido-4-octadecen-1,3-diol 在 吡啶 、 四丁基氟化铵 、 sodium iodide 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 7.0h， 生成 Benzoic acid (E)-(R)-1-[(R)-1-(2,2-dichloro-acetylamino)-2-iodo-ethyl]-hexadec-2-enyl ester
  参考文献：
  名称：

  Synthesis of fluorescent and radioactive analogues of two lactosylceramides and glucosylceramide containing β-thioglycosidic bonds that are resistant to enzymatic degradation

  摘要：

  Condensation of 2-S-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-2-thiopseudourea hydrobromide with 2,3,6-tri-O-benzoyl-4-O-trifluoromethylsulfonyl-beta-D-galactopyranosy-(1-->1)-(2S,3R,4E)-3-O-benzoyl-2-dichloroacetamido-4-octadecan afforded S-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-(1-->4)-2,3,6-tri-O-benzoyl-4-thio-beta-D-glucopyranosyl-(1-->1)-(2S, 3R,4E)-3-O-benzoyl-2-dichloroacetamido-4 in good yield. Removal of the protecting groups, followed by selective N-acylation of the sphingosine amino group with either a fluorescent or a radioactive fatty acid, gave labeled lactosylceramide analogues in good yield. Since these products contained a beta-thioglycosidic bond between the two sugar moieties, they were totally resistant to the action of acid lysosomal glycosidases. Likewise, condensation of 2-S(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosy hydrobromide and 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl-(1-->4)-2,3,6-tri-O- acetyl-1-S-acetyl-1-thio-beta-D-glucopyranose with (2R,3R,4E)-3-O-benzoyl-2-dichloroacetamido-1-iodo-4-octadecen-3-ol in methanolic sodium acetate afforded the corresponding beta-thioglycosides 14 and 16, respectively, in good yield. These beta-thioglycosides were converted into glucosylceramide and lactosylceramide analogues following removal of the protecting groups and by subsequent selective N-acylation using either a fluorescent or radioactive fatty acid N-succinimidyl ester. Whereas the glucosylthioceramides thus obtained proved to be completely undegradable by lysosomal glucocerebrosidase, the lactosylceramides containing the beta-thioglycosidic bond between the lactose and the ceramide residues could be degraded by lysosomal GM1-beta-galactosidase to give the corresponding glucosylthioceramides. These compounds did not yield to any further enzymatic degradation.

  DOI：

  10.1016/0008-6215(95)00189-z

文献信息

• Synthesis of ganglioside GM1 containing a thioglycosidic bond to its labeled ceramide(s). A facile synthesis starting from natural gangliosides
  作者：Günter Schwarzmann、Petra Hofmann、Ute Pütz

  DOI：10.1016/s0008-6215(97)00202-4

  日期：1997.10

  Capitalizing on the readily available ganglioside, GM1, we have devised a simple synthesis of labeled GM1 analogues with sulfur in place of oxygen in their linkage to the ceramide residue (SGM1). The sugar moiety of ganglioside GM1 was released by ozonolysis and subsequent alkaline fragmentation in good yield. During acetylation of the ganglioside sugar, the carboxyl group of the sialic acid residue

  利用容易获得的神经节苷脂GM1，我们设计了一种标记的GM1类似物的简单合成方法，该类似物用硫代替氧来连接神经酰胺残基（SGM1）。神经节苷脂GM1的糖部分通过臭氧分解和随后的碱裂解以良好的产率释放。在神经节苷糖的乙酰化过程中，唾液酸残基的羧基被内半乳糖部分（半乳糖II）的2-羟基内酯化。十五烷-O-乙酰基-单唾液酸神经节四糖的所得唾液酰基-II2-内酯可以容易地转化为α-糖基溴化物。随后用硫代乙酸钾处理该糖基溴化物，得到十四烷基-O-乙酰基-1-S-乙酰基-1-硫代-β-单唾液酸神经四糖的唾液酰基-II2-内酯。后者可以与（2R，3R，在乙酸甲醇钠中的4E）-3-O-苯甲酰基-2-二氯乙酰胺基-1-碘-4-十八烷基-3-醇，得到保护的溶血-SGM1衍生物。在碱性条件下一步除去保护基，得到β-单唾液酸血管神经四糖基硫代鞘氨醇。分别使用放射性碳标记的辛酸和十八烷酸的N-琥珀酰亚胺基衍生物将该溶