phenyl 4-O-benzoyl-1-thio-α-L-rhamnopyranoside | 145836-09-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 4-O-benzoyl-1-thio-α-L-rhamnopyranoside
• CAS: 145836-09-5
• 化学式: C₁₉H₂₀O₅S
• 分子量: 360.431
• InChiKey: VOIKTZDVDWIWPP-ISGVQESYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.47
• 重原子数：
  25.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  75.99
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  phenyl 4-O-benzoyl-1-thio-α-L-rhamnopyranoside 在 吡啶 、 溴 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 3.0h， 生成 4-O-benzoyl-2,3-O-carbonyl-α-L-rhamnopyranosyl bromide
  参考文献：
  名称：

  The 3,4-O-Carbonate Protecting Group as a β-Directing Group in Rhamnopyranosylation in Both Homogeneous and Heterogeneous Glycosylations As Compared to the Chameleon-like 2,3-O-Carbonates

  摘要：

  It is demonstrated that the beta-selectivity observed in the insoluble silver salt mediated couplings of 2,3-O-carbonate-protected rhamnosyl bromides is uniquely due to the heterogeneous nature of the reaction. In homogeneous solution these same donors are alpha-selective, a fact that is attributed to the half-chair conformation of these substances which reduces the energy barrier to oxacarbenium ion formation. It is suggested that the 2,3-O-carbonate group be dubbed torsionally arming in the manno- and rhamnopyranose series. When the carbonate group is removed to the 3,4-O-position a beta-selective system is formed, in both homogeneous and heterogeneous conditions, and it is demonstrated that this selectivity arises from the combination of the electron-withdrawing nature of the carbonate and its inability to take part in neighboring participation.

  DOI：

  10.1021/jo035003j
• 作为产物：
  描述：

  phenyl 2,3,4-tri-O-acetyl-1-thio-α-L-rhamnopyranoside 在 吡啶 、 D(+)-10-樟脑磺酸 、 sodium methylate 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 6.08h， 生成 phenyl 4-O-benzoyl-1-thio-α-L-rhamnopyranoside
  参考文献：
  名称：

  一种在合成硫代糖苷2,3-原酸酯过程中避免烷硫基迁移的简单方法。部分酰化的1-硫代-α-L-鼠李糖吡喃糖苷的改进合成。

  摘要：

  DOI：

  10.1016/0008-6215(92)80098-l

文献信息

• Stereoselective synthesis of 2-S-ethyl(phenyl)-2-thio-β-glucopyranosides via 1,2-migration and concurrent glycosidation of ethyl(phenyl) 2,3-orthoester-1-thio-α-mannopyranosides
  作者：Zunyi Yang、Biao Yu

  DOI：10.1016/s0008-6215(01)00124-0

  日期：2001.7

  Abstract 1,2-Migration and concurrent glycosidation of ethyl(phenyl) 2,3-orthoester-1-thio-α- d - and l -mannopyranosides under the action of TMSOTf readily afforded the corresponding 2- S -ethyl(phenyl)-2-thio-β-glucopyranosides, ready precursors to 2-deoxy- arabino -hexopyranosides (2-deoxy-β-glucopyranosides).

  摘要在TMSOTf作用下，乙基（苯基）2，3-原酸酯-1-硫代α-d-和1-甘露吡喃糖苷的1,2-迁移和同时的糖基化反应很容易得到相应的2-S-乙基（苯基）- 2-硫代-β-吡喃葡萄糖苷，是2-脱氧-阿拉伯糖基-己吡喃糖苷（2-脱氧-β-吡喃葡萄糖苷）的现成前体。
• Total Synthesis of Lobatoside E, A Potent Antitumor Cyclic Triterpene Saponin
  作者：Chunsheng Zhu、Pingping Tang、Biao Yu

  DOI：10.1021/ja801669r

  日期：2008.5.1

  Lobatoside E, a novel and complex cyclic triterpene saponin showing potent antitumor activities, has been synthesized for the first time, employing a highly modular approach. The synthesis, starting with oleanolic acid, D-glucose, D-galactose, L-arabinose, and L-rhamnose, requires a total of 73 steps, with the longest linear sequence of 31 steps and in 1.2% overall yield.

  Lobatoside E 是一种新型复杂的环状三萜皂苷，具有强大的抗肿瘤活性，是首次采用高度模块化的方法合成。该合成从齐墩果酸、D-葡萄糖、D-半乳糖、L-阿拉伯糖和 L-鼠李糖开始，总共需要 73 个步骤，最长的线性序列为 31 个步骤，总产率为 1.2%。
• Synthesis and Biological Evaluation of O‐Methylated Glycolipids Related to PGLs via Direct Stereoselective Glycosidation and Sequential Suzuki–Miyaura Coupling using Boracyclane
  作者：Ko Sato、Zakaria Omahdi、Kensuke Shibata、Koh‐hei Sonoda、Sho Yamasaki、Hiroshi Tanaka

  DOI：10.1002/chem.201703684

  日期：2017.11.16

  methodology improved the efficiency of the synthesis of both PGL‐1 and PGL‐tb1 sugars. The process involved the formation of 2‐O‐naphthylmethyl‐α‐rhamnoside and 2‐O‐methyl‐α‐fucoside. Sequential Suzuki–Miyaura coupling using synthetic glycosides, boracyclane, and aryl bromides provided glycolipids related to PGL sugars, and was accomplished with a one‐pot process. Finally, we elucidated the immunosuppressive

  报道了通过直接立体选择性糖苷合成的O-甲基化糖脂，其糖基与酚类糖脂（PGLs）中的糖基有关。用I 2和n Bu 4 NOTf处理2 - O-甲基鼠李糖苷酰亚胺可导致它们在低温下活化，并为α-鼠李糖苷提供出色的α-选择性。n Bu 4 NOTf增强了碘的亲电性。这种方法提高了PGL-1和PGL-tb1糖的合成效率。该过程涉及2 - O-萘甲基-α-鼠李糖苷和2- O的形成-甲基-α-岩藻糖苷。使用合成糖苷，硼环烷和芳基溴化物的顺序Suzuki-Miyaura偶联提供了与PGL糖相关的糖脂，并通过一锅法完成。最后，我们阐明所有这些合成的化合物的免疫抑制活性，发现苯基3- ö -α鼠李糖-2- ø -甲基- α鼠李糖苷具有一个6-（2-萘基）己基表现最强的抑制效果。
• A novel and expeditious approach to the stereoselective synthesis of 2-S-ethyl(phenyl)-2-deoxy-β-glycosides, ready precursors to 2-deoxy-β-glycosides
  作者：Biao Yu、Zunyi Yang

  DOI：10.1016/s0040-4039(00)00281-1

  日期：2000.4

  1,2-Migration and concurrent glycosidation of ethyl(phenyl) 2,3-orthoester-1-thio-alpha-1-rhamnopyranosides under the action of TMSOTf readily afforded the corresponding 2-S-ethyl(phenyl)-2-deoxy-beta-glycosides, ready precursors to 2-deoxy-beta-glycosides. (C) 2000 Elsevier Science Ltd. All rights reserved.