1,3,4-tri-O-acetyl-L-rhamnopyranose | 57794-09-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,3,4-tri-O-acetyl-L-rhamnopyranose
• 英文别名: 1,3,4-tri-O-acetyl-2-deoxy-L-arabino-hexopyranose；1,3,4-tri-O-acetyl-2,6-dideoxy-L-arabino-hexopyranose；1,3,4-tri-O-acetyl-2-deoxy-L-rhamnopyranose；1,3,4-tri-O-acetyl-2,6-dideoxy-L-rhamnose；1,3,4-tri-O-acetyl-2-deoxy-L-rhamnopyranoside；[(2S,3S,4S)-3,6-diacetyloxy-2-methyloxan-4-yl] acetate
• CAS: 57794-09-9
• 化学式: C₁₂H₁₈O₇
• 分子量: 274.271
• InChiKey: QKPIXQGRPBEVLX-RFDDSKSZSA-N

物化性质

• 沸点：
  333.1±42.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1,3,4-tri-O-acetyl-L-rhamnopyranose 在 sodium hydroxide 、 六氟磷酸银 、 4 A molecular sieve 、 三氟化硼乙醚 、 2,4,6-三叔丁基嘧啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 7-[4-O-(2,6-dideoxy-α-L-arabino-hexopyranosyl)-3-azido-2,3,6-trideoxy-α-L-lyxo-hexopyranosyl]daunorubicinone
  参考文献：
  名称：

  Syntheses and Biological Activities of 3‘-Azido Disaccharide Analogues of Daunorubicin against Drug-Resistant Leukemia

  摘要：

  Anthracyclines, such as daunorubicin (DNR) and doxorubicin (Dox), are widely used for cancer therapy but are limited by drug resistance and cardiotoxicity. To overcome drug resistance, we synthesized a novel class of disaccharide analogues of DNR against drug-resistant leukemia. In these disaccharide analogues (1-6) the first (inner) sugar in the carbohydrate chain is a 3-azido-2,3,6-trideoxy-L-lyxo-alpha-hexopyranose; the second (outer) sugars that are linked via alpha(1 -> 4) to the first sugar are a series of uncommon sugars. Their cytotoxicities were examined in drug-sensitive leukemia cells K562 and doxorubicin-resistant K562/Dox cells by MTS assay. In drug-sensitive cells, compounds 1-6 were found to be active against leukemia K562 cells with IC50 in the nanomolar range (200-1100 nM), while compounds 2-5 with 2,6-dideoxy sugars showed better activity than compounds 1 and 6 with 2,3,6-trideoxy sugars. In doxorubicin-resistant K562/Dox cells, compounds 1, 3, and 5 exhibited much better activities (with IC50 between 0.29 and 2.0 mu M) than DNR (with IC50 > 5 mu M). Compound 3 emerged as the most active compound, showing at least 17-fold higher activity against drug-resistant cells than parent compound DNR. The IC50 values of compound 3 in both drug-sensitive and drug-resistant cells are identical, which indicates that compound 3 completely overcomes drug resistance. Structure-activity relationship (SAR) studies showed that the substitution and orientation of the 3-OH group in the second sugar significantly influence its activity against drug-resistant leukemia. These results suggest that sugar modifications of anthracyclines change their activity and overcome drug resistance.

  DOI：

  10.1021/jm050916m
• 作为产物：
  描述：

  溶剂黄146 、 3,4-二-O-乙酰-1,5-酐-2,6-双脱氧-L-阿拉伯-己-1-糖醇 在 三苯基膦氢溴酸盐 作用下， 以 二氯甲烷 为溶剂， 反应 40.0h， 以72%的产率得到1,3,4-tri-O-acetyl-L-rhamnopyranose
  参考文献：
  名称：

  糖肽糖基转移酶合成效用的系统研究

  摘要：

  参与细菌次级代谢产物生物合成的糖基转移酶可用于生成生物活性天然产物的糖修饰类似物。一些糖基转移酶具有宽松的底物特异性，并且已经假定滥交是该类的一个特征。作为探索这些酶合成效用计划的一部分，我们使用纯化的酶和化学合成的 TDP β- 分析了将类似的 2-脱氧-L-糖连接到万古霉素型糖肽苷元的糖基转移酶的底物选择性。 2-脱氧-L-糖类似物。我们表明，虽然这些糖肽糖基转移酶中的一些是混杂的，但其他糖肽糖基转移酶只能容忍它们将处理的底物的微小修改。例如，糖基转移酶 GtfC 和 GtfD，分别将 4-epi-L-vancosamine 和 L-vancosamine 转移到万古霉素假糖苷和氯定向素 B 的葡萄糖单元的 C-2，显示出适度放松的供体底物特异性对其天然苷元的糖基化。相比之下，GtfA，一种将 4-epi-L-vancosamine 连接到苄基位置的转移酶，仅利用与其天然 TDP 糖底

  DOI：

  10.1021/ja052945s

文献信息

• Synthesis and collagenase inhibition of new glycosides of aranciamycinone: the aglycon of the naturally occurring antibiotic aranciamycin
  作者：Mikael Bols、Lise Binderup、Jytte Hansen、Poul Rasmussen

  DOI：10.1016/0008-6215(92)80084-e

  日期：1992.11

  beta-D-xylopyranose, alpha-L-fucopyranose, 2-azido-2,6-dideoxy-alpha-L-mannopyranose, 2,6-dideoxy-alpha-L-arabino-hexopyranose, 3,6-dideoxy-alpha-L-arabino-hexopyranose, and 4,6-dideoxy-alpha-L-lyxo-hexopyranose. The new glycosides were tested for inhibition of Clostridium histolyticum collagenase and Yoshida Sarcoma tumor cells.

  通过用乙酸乙酸酯和三氟甲磺酸三甲基甲硅烷基酯在二氯甲烷中的糖基化作用来制备阿拉伯衣霉素的糖苷。制备了以下糖的糖苷：α-L-鼠李吡喃糖，β-D-吡喃葡萄糖，β-D-核吡喃糖，β-D-木吡喃糖，α-L-呋喃二糖，2-叠氮基-2,6-二脱氧-α- L-甘露吡喃糖，2,6-二脱氧-α-L-阿拉伯糖-己糖，3,6-二脱氧-α-L-阿拉伯糖-己糖和4,6-二脱氧-α-L-lyxo-己糖。测试了新糖苷对溶组织梭状芽孢杆菌胶原酶和吉田肉瘤肿瘤细胞的抑制作用。
• 一种含2-脱氧鼠李糖的角环素类似物的制备方法
  申请人：华东师范大学

  公开号：CN110183427A

  公开（公告）日：2019-08-30

  本发明公开了一种含2‑脱氧鼠李糖的角环素类似物的制备方法，其特点是采用2‑脱氧全乙酰化鼠李糖经过碳糖苷化、乙酰化、N‑溴代丁二酰亚胺溴代、Diesl‑Alder反应，合成具有生物活性分子的含2‑脱氧鼠李糖苷的角环素类似物。本发明与现有技术相比具有生物活性分子，合成路线简洁高效，每步转化反应时间短，操作更为简便，产率高，总收率为42.2%，所用试剂廉价易得，生产成本低，有机溶剂和催化剂用量较少，生产成本低，有效地避免了高毒试剂的使用，是一种绿色环保、经济高效制备含2‑脱氧鼠李糖的角环素类似物的方法。
• Synthetic Approaches to the Angucycline Antibiotics. A Route to C-Glycosidic Benz[a]anthraquinones
  作者：Fleur L. Andrews、David S. Larsen、Lesley Larsen

  DOI：10.1071/ch99124

  日期：——

  3-Deoxy-6′-hydroxy-13-norurdamycinone B (32a) and 3-deoxy-13-norurdamycinone B (32b) have been synthesized in eight steps from 5,8-dimethoxynaphthalen-1-ol (9) both in 28% overall yield. The key step in this approach is the boron trifluoride diethyl etherate promoted β-C-glycosylations of (9) and 1,3,4,6-tetra-O-acetyl-2-deoxy- and 1,3,4-tri-O-acetyl-2-deoxy-D-arabino-hexopyranoses (13) and (19). The solvent, acetonitrile, was essential for the success of these reactions. Acetylation of the C-glycosyl-5,8-dimethoxynaphthalen-1-ols (16) and (20) followed by oxidation with ceric ammonium nitrate gave C-glycosyl-5-acetoxy-1,4-naphthoquinone derivatives (21) and (23) in 63 and 49% overall yields from (9). Selective deacetylation of the C 5 acetoxy groups of (21) and (23) was achieved by treatment with boron trifluoride etherate in dichloromethane to give 3,4,6-tri-O-acetyl- 2-deoxy- and 3,4-di-O-acetyl-2,6-dideoxy-β-D-arabino-hexopyranosyl-5-hydroxy-1,4-naphthoquinones (24) and (25) respectively. The tetra-O-acetyl diborate promoted Diels–Alder reactions of (24) and (25) with (±)-(E)-1-acetoxy-3-(2-methoxyvinyl)cyclohex-2-ene (8) each gave a 1 : 1 mixture of diastereoisomeric cycloadducts which, upon treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene gave (1R*)-1-acetoxy-9-(3,4,6-tri-O-acetyl-2-deoxy-β-D-arabino-hexopyranosyl)- and (1R*)-1-acetoxy-9-(3,4-di-O-acetyl-2,6-dideoxy-β-D-arabino-hexopyranosyl)-8-hydroxy-1,2,3,4-tetrahydrobenz[a]anthracene-7,12-dione (30a) and (30b) respectively. Sequential deacetylation and photochemical oxidation of (30a) and (30b) gave the targets (32a) and (32b) respectively.

  3-脱氧-6′-羟基-13-去甲达姆霉素 B（32a）和 3-脱氧-6′-羟基-13-去甲达玛霉素酮 B（32a）和 3-脱氧-13-去甲达玛霉素酮 B（32b）是由 5,8-二甲氧基萘-1-醇 (9) 经过八个步骤合成的，总收率为 28%。该方法的 的关键步骤是用三氟化硼二乙基醚促进 的β-C-糖基化反应。 1,3,4,6-tetra-O-acetyl-2-deoxy- and 1,3,4-O-三乙酰基-2-脱氧-D-阿拉伯并六吡喃糖 (13) 和 (19)。溶剂乙腈对这些反应的成功至关重要。 溶剂乙腈对这些反应的成功至关重要。乙酰化 C-糖基-5,8-二甲氧基萘-1-醇 (16) 和 (20) 的乙酰化反应，然后用铈氨氧化。 然后用硝酸铈铵氧化，得到 C-糖基-5-乙酰氧基-1,4-萘醌衍生物（21） 和 (23)，总产率分别为 63% 和 49%。选择性脱乙酰化 三氟化硼醚化物处理，实现了对(21)和(23)的 C 5 乙酰氧基的选择性脱乙酰化。 在二氯甲烷中用三氟化硼醚酸盐处理，得到 3,4,6-三-O-乙酰基-2-脱氧基和 3,4,6-三-O-乙酰基-2-脱氧-β-D-阿拉伯并六吡喃糖基-5-羟基-1,4-萘醌 (24) 和 (25)。四-O-乙酰基二硼酸盐 促进了 (24) 和 (25) 与以下物质的 Diels-Alder 反应 (±)-(E)-1-乙酰氧基-3-(2-甲氧基乙烯基)环己-2-烯 (8) 的 Diels-Alder 反应。 (8) 的非对映异构环加成物的 1 : 1 混合物。 用 1,8-二氮杂双环[5.4.0]十一-7-烯处理后，得到 (1R*)-1-acetoxy-9-(3,4,6-tri-O-acetyl-2-deoxy-β-D-arabino-hexopyranosyl)- 和 (1R*)-1-乙酰氧基-9-(3,4-二-O-乙酰基-2,6-二脱氧-β-D-阿拉伯己吡喃糖基)-8-羟基-1,2,3,4-四氢苯并[a]蒽-7,12-二酮 分别为 (30a) 和 (30b)。(30a)和(30b)的顺序脱乙酰化和光化 (30a)和(30b)的顺序脱乙酰化和光化学氧化，分别得到目标物(32a)和(32b)。
• Synthetic approaches to the angucycline antibiotics: Synthesis of the C-glycosidic CD ring system
  作者：Fleur L. Andrews、David S. Larsen

  DOI：10.1016/s0040-4039(00)78474-7

  日期：1994.11

  system of the angucycline antibiotics and analogues thereof are reported. The key step in their preparation was the C-glycosylation reaction of 5-hydroxy-1,4-dimethoxynaphthalene and a series of 1-O-acyl-2-deoxy and 1-O-acyl-2, 6-dideoxy sugar electrophiles promoted by boron trifluoride etherate. The use of the participating solvent, acetonitrile, was essential for the success of the reaction.

  报道了环霉素抗生素及其类似物的保护的C-糖基取代的CD环系统的合成。它们制备的关键步骤是5-羟基-1,4-二甲氧基萘与一系列促进1 - O-酰基-2-脱氧和1 - O-酰基-2,6-二脱氧糖亲电试剂的C-糖基化反应由三氟化硼醚化。参与溶剂乙腈的使用对于反应成功是必不可少的。
• 一种β-2,6-二脱氧糖芳基-C-糖苷的制备方法
  申请人：华东师范大学

  公开号：CN106967023B

  公开（公告）日：2019-09-10

  本发明公开了一种β‑2,6‑二脱氧糖芳基‑C‑糖苷的制备方法，其特点是以不同保护基取代的脱氧糖为给体，1‑萘酚、2‑萘酚、4‑甲氧基‑1‑萘酚、5‑甲氧基‑1‑萘酚或1,5‑二甲氧基萘为受体，将给体与受体按1:1.0~5.0的当量比混合，搅拌下加入乙腈、二氯甲烷或1,2‑二氯乙烷，然后在I2‑Et3SiH催化体系下进行糖苷化反应。本发明与现有技术相比具有工艺简单、操作方便，生产成本低，产率高，立体选择性高，反应条件更温和，反应时间短等优点，避免了高毒化学原料对环境的污染，是一种受体底物适用范围更广、绿色环保和经济高效的β‑2,6‑二脱氧糖芳基‑C‑糖苷制备方法。