1-(3',4',6'-tri-O-acetyl-2'-deoxy-β-D-arabino-hexopyranosyl)naphthalen-2-ol | 142061-25-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-(3',4',6'-tri-O-acetyl-2'-deoxy-β-D-arabino-hexopyranosyl)naphthalen-2-ol
• 英文别名: 2-hydroxy-1-(3',4',6'-tri-O-acetyl-2'-deoxy-β-D-glucopyranosyl)naphthalene
• CAS: 142061-25-4
• 化学式: C₂₂H₂₄O₈
• 分子量: 416.428
• InChiKey: PFERNSJUXWAGDV-VMBXEPDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  30.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  108.36
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为产物：
  描述：

  3,4,6-O-三乙酰基-2-脱氧-D-葡萄糖 在 三氟化硼乙醚 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 生成 1-(3',4',6'-tri-O-acetyl-2'-deoxy-β-D-arabino-hexopyranosyl)naphthalen-2-ol
  参考文献：
  名称：

  Synthetic Approaches to the Angucycline Antibiotics. A Route to C-Glycosidic Benz[a]anthraquinones

  摘要：

  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)。

  DOI：

  10.1071/ch99124

文献信息

• A Metal-Free β-Stereoselective Synthesis of 2-Deoxy-C-arylglycosides: Synthesis of 5-Aza Analogues of Aquayamycin
  作者：Jianbo Zhang、Yuling Mei、Nan Jiang、Yu Yang、Wan Zhang、Saifeng Qiu、Hong Guo

  DOI：10.1055/a-1670-2290

  日期：2021.12

  A convenient protocol for the β-stereoselective synthesis of 2-deoxy-C-arylglycosides has been developed. This reaction takes place in one step by using I2/Et3SiH to activate a glycosyl acetate to generate a glycosyl iodide intermediate in situ, which is captured by a naphthol; this is followed by a Fries-like O-to-C glycoside rearrangement to afford a β-C-aryl glycoside selectively. The approach is applicable to a wide range of naphthol moieties, and its utility was demonstrated in syntheses of 5-aza analogues of aquayamycin.

  标题：摘要 已开发了一种用于β-立体选择性合成2-去氧-C-芳基糖苷的便捷方案。该反应通过使用I2/Et3SiH在一步中激活糖醋酸酯以生成原位的糖基碘中间体，该中间体被萘酚捕获；随后进行类Fries的O到C糖苷重排，选择性地生成β-C-芳基糖苷。该方法适用于广泛的萘酚基团，并且其实用性已在合成5-氮杂环丙霉素类似物中得到证明。
• An imrpoved practical method for synthesis of aryl C-glycosides from unprotected methyl glycosides and 1-hydroxy sugars
  作者：Kazunobu Toshima、Goh Matsuo、Masaya Nakata

  DOI：10.1039/c39940000997

  日期：——

  Aryl C-glycosidations of the unprotected methyl glycosides 9–12 and the unprotected 1-hydroxy sugars 14 and 15 with 2-naphthol 6 using TMSOTf proceed much more effectively than those of the acylated methyl glycosides 4 and 5; the unprotected methyl glycoside 10 is also smoothly coupled with other phenol and naphthol derivatives 25–27 to give the corresponding unprotected o-hydroxyaryl β-C-glycosides

  使用TMSOTf对未保护的甲基糖苷9-12和未保护的1-羟基糖14和15以及2-萘酚6进行芳基C糖基化作用比酰化的甲基糖苷4和5更为有效。未保护的甲基糖苷10还可与其他苯酚和萘酚衍生物25-27平滑偶联，从而以高收率获得相应的未保护的邻羟基芳基β- C-糖苷（TMSOTf =三甲基甲硅烷氧基三氟甲磺酸酯）。
• 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。
• Aryl and Allyl <i>C</i>-Glycosidation Methods Using Unprotected Sugars
  作者：Kazunobu Toshima、Goh Matsuo、Toru Ishizuka、Yasunobu Ushiki、Masaya Nakata、Shuichi Matsumura

  DOI：10.1021/jo972146v

  日期：1998.4.1

  Practical and highly stereoselective aryl and allyl C-glycosidation methods using unprotected sugars as glycosyl donors have been developed. Aryl C-glycosidations of several unprotected 2-deoxy sugars with phenol and naphthol derivatives by the combined use of trimethylsilyl trifluoromethanesulfonate (TMSOTf)-AgClO4 or TMSOTf exclusively gave the corresponding unprotected o-hydroxyaryl beta-C-glycosides which appear in many biologically attractive aryl C-glycoside antibiotics as the key subunit. On the other hand, allyl C-glycosidations of several unprotected glycals with allyltrimethylsilane by TMSOTf afforded the corresponding unprotected and 2,3-unsaturated allyl alpha-C-glycosides in high yields which are versatile synthetic intermediates for the syntheses of optically active natural products.
• Efficient C-arylglycosylation of 1-O-methyl sugar by novel use of TMSOTf-AgClO4 catalyst system
  作者：Kazunobu Toshima、Goh Matsuo、Kuniaki Tatsuta

  DOI：10.1016/0040-4039(92)88170-a

  日期：1992.4

  Highly beta-stereoselective C-arylglycosylations of the 1-O-methyl sugars 1 approximately 4 with 2-naphthol (9) were effectively achieved by novel combinational use of a catalytic amount of TMSOTf-AgClO4 as an activator. Also, C-arylglycosylations of the 1-O-acetyl sugars 5 approximately 8 with 9 in this way worked as well.