methyl 2-O-trichloroacetyl-3,4-di-O-acetyl-β-D-glucuronatopyranosyl | 148695-04-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-O-trichloroacetyl-3,4-di-O-acetyl-β-D-glucuronatopyranosyl
• 英文别名: methyl (2S,3S,4S,5R,6S)-3,4-diacetyloxy-6-chloro-5-(2,2,2-trichloroacetyl)oxyoxane-2-carboxylate
• CAS: 148695-04-9
• 化学式: C₁₃H₁₄Cl₄O₉
• 分子量: 456.061
• InChiKey: FJENVYCCSMLUHK-GENCIFFESA-N

物化性质

• 沸点：
  415.0±45.0 °C(Predicted)
• 密度：
  1.56±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl 2-O-trichloroacetyl-3,4-di-O-acetyl-β-D-glucuronatopyranosyl 在 氨 作用下， 以 乙醚 为溶剂， 反应 0.17h， 以84.4%的产率得到methyl 3,4-di-O-acetyl-β-D-glucuronatopyranosyl chloride
  参考文献：
  名称：

  β-和α-吡喃葡萄糖过乙酸盐与PCl5的反应，并利用产物构建sarsasapogenin糖苷。

  摘要：

  β-和α-吡喃葡萄糖过乙酸盐与PCl5的反应产生了区域选择性氯化的产物。1,2,3,4,6-戊基-O-乙酰基-β-D-吡喃葡萄糖（5）和-β-D-吡喃半乳糖（6）与PCl5在CCl4中的反应和甲基2,3,4 -三-O-乙酰基-β-D-葡萄糖醛酸吡喃葡萄糖（7）与PCl5在甲苯中的主要产物分别为2-O-三氯乙酰基-β-D-吡喃糖基氯4，12和14，以及α-D-吡喃糖基氯化物11、13和15分别作为次要产品。另一方面，分别为5和6的α-端基异构体的化合物8和9与PCl5的反应得到的主要产物是将C-6处的乙酰基转化为-C（Cl）= CCl2或-C（Cl ）2-CCl3基团（8和16分别来自8和18和9）。10的相同反应是7的α-端基异构体，产生的α-氯化物15为主要产物。糖衍生物4与sarsasapogenin 23的糖苷化反应产生β-糖苷24（29.1％）和α-糖苷25（46.9％），12与23的糖苷化反应产生β-糖苷26（24

  DOI：

  10.1248/cpb.40.3261
• 作为产物：
  描述：

  methyl 1,2,3,4-tetraacetyl-α-D-glucopyranuronate 在 五氯化磷 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以5.3%的产率得到methyl 2-O-trichloroacetyl-3,4-di-O-acetyl-β-D-glucuronatopyranosyl
  参考文献：
  名称：

  β-和α-吡喃葡萄糖过乙酸盐与PCl5的反应，并利用产物构建sarsasapogenin糖苷。

  摘要：

  β-和α-吡喃葡萄糖过乙酸盐与PCl5的反应产生了区域选择性氯化的产物。1,2,3,4,6-戊基-O-乙酰基-β-D-吡喃葡萄糖（5）和-β-D-吡喃半乳糖（6）与PCl5在CCl4中的反应和甲基2,3,4 -三-O-乙酰基-β-D-葡萄糖醛酸吡喃葡萄糖（7）与PCl5在甲苯中的主要产物分别为2-O-三氯乙酰基-β-D-吡喃糖基氯4，12和14，以及α-D-吡喃糖基氯化物11、13和15分别作为次要产品。另一方面，分别为5和6的α-端基异构体的化合物8和9与PCl5的反应得到的主要产物是将C-6处的乙酰基转化为-C（Cl）= CCl2或-C（Cl ）2-CCl3基团（8和16分别来自8和18和9）。10的相同反应是7的α-端基异构体，产生的α-氯化物15为主要产物。糖衍生物4与sarsasapogenin 23的糖苷化反应产生β-糖苷24（29.1％）和α-糖苷25（46.9％），12与23的糖苷化反应产生β-糖苷26（24

  DOI：

  10.1248/cpb.40.3261

文献信息

• Preparation of Glycyrrhetic Acid .BETA.-Glycosides Having .BETA.(1.RAR.2)-Linked Disaccharides by the Use of 2-O-Trichloroacetyl-.BETA.-D-pyranosyl Chlorides and Their Cytoprotective Effects on Hepatic Injury in Vivo.
  作者：Setsuo SAITO、Yuka SASAKI、Kaoru KURODA、Yasunobu HAYASHI、Shigeya SUMITA、Yoichi NAGAMURA、Keiji NISHIDA、Isao ISHIGURO

  DOI：10.1248/cpb.41.539

  日期：——

  Stepwise glycosidation was adopted for the construction of glycyrrhetic acid β-glycosides (27-30) having β(1→2)-linked disaccharides such as 2-O-β-D-flucuronopyranosyl-β-D-glucopyranose, 2-O-β-D-glucuronopyranosyl-β-D-galactopyranose, 2-O-β-D-glucopyranosyl-β-D-glucuronopyranose and 2-O-β-D-galactopyranosyl-β-D-glucuronopyranose. In the first glycosidation, 2-O-trichloroacety-β-D-pyranosyl chlorides (9-11) were utilized as starting sugar derivatives to react with methyl glycyrrhetinate (5) : Glycosidation of 5 with 9 and 10 gave β- and α-monoglycosides (12) and (13), and (15) and (16), respectively. Treatment of the β-glycoside 12 and 15 with ammonia-saturated ether gave products (14) and (17), respectively. The glycosidation of 5 with 11 followed by treatment with ammonia-saturated ether gave compounds (18) and (19), respectively. The second step glycosidations of 14 and 17 with methyl 2, 3, 4-tri-ο-acetyl-α-D-glucuronatopyranosyl bromide (20) gave diglycoside derivatives (23) and (24), respectively, and that of 18 with 2, 3, 4, 6-tetra-O-acetyl-α-D-glucopyranosyl bromide (21) and -α-D-galactopyranosyl bromide (22) gave deglycoside derivatives (25) and (26), respectively. The removal of the protecting groups of 23-26 gave diglycosides 27-30, respectively, having a β-D-glucuronopyranose (β-D-glcUA) as one of two sugar components in the molecules. The cytoprotective effects of the synthesized glycosides 27-30 on carbon tetrachloride (CCl4)-induced hepatotoxicity in vivo were compared with deglycosides 31-33 having only neutral sugar components, and naturally occurring glycyrrhizin (34) having two acidic sugar components (β-D-glcUA). While glycosides 31-33 had no cytoprotective effect, glycosides 27-30 showed potent effects. Especially, 27 and 28, having a β-D-glcUA as the terminal sugar component, were more effective meterials against hepatic injury than glycyrrhizin 34.

  采用分步糖苷化法构建了具有β(1→2)连接的二糖的甘草酸β-糖苷（27-30），这些二糖包括2-O-β-D-氟尿喹喃糖基-β-D-葡萄糖、2-O-β-D-古糖喹喃糖基-β-D-半乳糖、2-O-β-D-葡萄糖喹喃糖基-β-D-古糖和2-O-β-D-半乳糖喹喃糖基-β-D-古糖。在第一次糖苷化中，使用了2-O-三氯乙酰-β-D-吡喃糖氯化物（9-11）作为起始糖衍生物，与甘草酸甲酯（5）反应：5与9和10的糖苷化分别得到了β-和α-单糖苷（12）和（13），以及（15）和（16）。 β-糖苷12和15与氨饱和醚反应后分别得到产物（14）和（17）。5与11的糖苷化，再与氨饱和醚反应，分别得到了化合物（18）和（19）。14和17与甲基2, 3, 4-三-O-乙酰-α-D-古糖喹喃糖溴化物（20）的第二步糖苷化分别得到二糖苷衍生物（23）和（24），而18与2, 3, 4, 6-四-O-乙酰-α-D-葡萄糖喹喃糖溴化物（21）和-α-D-半乳糖喹喃糖溴化物（22）的糖苷化分别得到去糖苷衍生物（25）和（26）。去除23-26的保护基团分别得到二糖苷27-30，这些化合物在分子中有一个β-D-古糖喹喃糖（β-D-glcUA）作为两个糖组分之一。合成的糖苷27-30对四氯化碳（CCl4）诱导的肝毒性在体内的细胞保护作用与去糖苷31-33（只有中性糖组分）及天然存在的甘草苷（34，具有两个酸性糖组分 β-D-glcUA）进行了比较。虽然糖苷31-33没有细胞保护作用，但糖苷27-30显示出显著的作用。尤其是，27和28作为末端糖组分具有β-D-glcUA，比甘草苷34对肝损伤的保护效果更佳。
• Studies on synthesis and structure-activity relationships against cytoprotective activity of triterpenoidal diglycosides with an acid saccharide, d-glucopyranosuronic acid
  作者：S Saito、S Sumita、T Furumoto、J Ebashi、Y Sasaki、Y Nagamura、I Ishiguro

  DOI：10.1016/0223-5234(94)90073-6

  日期：1994.1

  Several triterpenoid alpha- and beta-diglycosides of oleanoic acid (1), 11-deoxoglycyrrhetic acid (4) and 11-deoxoglycyrrhetol (5) were synthesized. The synthetic diglycosides induced one or both D-glucopymanosuronic acids as sugar components. Cytoprotective activities of the diglycosides against carbon tetrachloride-induced hepatotoxicity were investigated using mice. The activities of the synthetic diglycosides were estimated by assay of aspartate transaminase and alanine transaminase, which were released from the injured hepatocytes and compared with that of glycyrrhizin (9). The beta-diglycosides of 1 and 4 showed potent activities in contrast to those of 5; none of the alpha-glycosides showed remarkable activity. Reduction of the carbonyl group (C=O) at C-11 on the C-ring of the aglycons slightly enhanced the activity over that of 9, and replacement of the carboxyl group (COOH) on the aglycons by a hydroxylmethyl group (CH2OH) drastically decreased the activity.