3,4-di-O-benzoyl-L-rhamnal | 34820-21-8

• 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: 3,4-di-O-benzoyl-L-rhamnal
• 英文别名: 1,5-anhydro-3,4-di-O-benzoyl-2,6-dideoxy-L-arabino-hex-1-enitol；[(2S,3S,4S)-3-benzoyloxy-2-methyl-3,4-dihydro-2H-pyran-4-yl] benzoate
• CAS: 34820-21-8
• 化学式: C₂₀H₁₈O₅
• 分子量: 338.36
• InChiKey: RKQVGBBRDUYLAT-WBAXXEDZSA-N

物化性质

• 沸点：
  468.7±45.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,4-di-O-benzoyl-L-rhamnal 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 1,2-双(二苯基膦)乙烷 吡啶 、 甲醇 、 N-溴代丁二酰亚胺(NBS) 、 三氟化硼乙醚 、 水 、 sodium hydride 、 戴斯-马丁氧化剂 、 对甲苯磺酸 、 copper(II) sulfate 、 环氧氯丙烷 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 乙二醇二甲醚 、 二氯甲烷 、 甲苯 、 苯 为溶剂， 反应 59.49h， 生成 (25R)-2α,2β,3β-[(2S,3S,4S,5S,6S)-tetrahydro-5-hydroxy-6-methyl-2H-pyran-4,3,2-trioxytriyl]-5α-spirostane
  参考文献：
  名称：

  Preparation of an analogue of orbicuside A, an unusual cardiac glycoside

  摘要：

  A steroid containing a multi-linked glycoside, analogous to the bufadienolide orbicuside A, has been prepared. The key steps were (i) the preparation of a 2alpha-allyloxycarbonyloxy-3beta-hydroxy steroid, (ii) a Ferrier reaction between the steroid and a rhamnal derivative, (iii) removal of protecting group and oxidation of the 2-hydroxy group, (iv) dihydroxylation of the pseudoglycal from the sterically more hindered side and finally (v) ring closure by acetal formation under acidic conditions. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.028
• 作为产物：
  描述：

  1,2,3,4-tetra-O-acetyl-L-rhamnopyranose 在 乙酸酐 吡啶 、 甲醇 、 氢溴酸 、 sodium acetate 、 乙酸酐 、 potassium carbonate 、 copper(II) sulfate 、 锌 作用下， 以 二氯甲烷 、 溶剂黄146 、 乙腈 为溶剂， 反应 52.0h， 生成 3,4-di-O-benzoyl-L-rhamnal
  参考文献：
  名称：

  Preparation of an analogue of orbicuside A, an unusual cardiac glycoside

  摘要：

  A steroid containing a multi-linked glycoside, analogous to the bufadienolide orbicuside A, has been prepared. The key steps were (i) the preparation of a 2alpha-allyloxycarbonyloxy-3beta-hydroxy steroid, (ii) a Ferrier reaction between the steroid and a rhamnal derivative, (iii) removal of protecting group and oxidation of the 2-hydroxy group, (iv) dihydroxylation of the pseudoglycal from the sterically more hindered side and finally (v) ring closure by acetal formation under acidic conditions. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.028

文献信息

• Sterically Hindered 2,4,6-Tri-<i>tert</i>-butylpyridinium Salts as Single Hydrogen Bond Donors for Highly Stereoselective Glycosylation Reactions of Glycals
  作者：Titli Ghosh、Ananya Mukherji、Pavan K. Kancharla

  DOI：10.1021/acs.orglett.9b00626

  日期：2019.5.17

  We demonstrate here that the strained and bulky protonated 2,4,6-tri-tert-butylpyridine salts serve as efficient catalysts for highly stereoselective glycosylations of various glycals. Moreover, the mechanism of action involves an interesting single hydrogen bond mediated protonation of glycals and not via the generally conceived Brønsted acid pathway. The counteranions also play a role in the outcome

  我们在这里证明，应变和庞大的质子化的2,4,6-三叔丁基吡啶盐可作为各种糖类的高度立体选择性糖基化的有效催化剂。此外，作用机理涉及有趣的单个氢键介导的糖基质子化，而不是通过通常构想的布朗斯台德酸途径。抗衡阴离子在反应结果中也起作用。
• Sterically Strained Brønsted Pair Catalysis by Bulky Pyridinium Salts: Direct Stereoselective Synthesis of 2-Deoxy and 2,6-Dideoxy-β-thioglycosides from Glycals
  作者：Ananya Mukherji、Rupa Bai Addanki、Suvendu Halder、Pavan K. Kancharla

  DOI：10.1021/acs.joc.1c02305

  日期：2021.12.3

  activation of a third molecule like thiol via hydrogen-bonding. This intriguing weak interaction-based reactivity has been utilized to develop an organocatalytic synthesis of 2-deoxy-β-thioglycosides from glycals. While the 1H NMR studies showcase the diamagnetic activation of thiols in the presence of the catalyst, the electron paramagnetic resonance (EPR) studies reveal the generation of a radical

  由空间庞大的碱 2,4,6-三叔丁基吡啶和盐酸获得的空间应变离子 Brønsted 对络合物对阴离子氯化物具有不寻常的反应性。大体积的邻叔丁基完全屏蔽阳离子 [N-H] +削弱了与氯阴离子可能的氢键相互作用，并且 [N-H] + ···Cl -距离异常长（3.10 Å）。这导致离子对之间的静电相互作用紧张/受挫，从而增加了两种离子的反应性，从而通过氢键激活了第三种分子（如硫醇）。这种有趣的基于弱相互作用的反应性已被用于开发从糖醛中有机催化合成 2-脱氧-β-硫糖苷的方法。虽然1H NMR 研究展示了在催化剂存在下硫醇的抗磁性活化，电子顺磁共振 (EPR) 研究揭示了自由基物种的产生，这表明可能存在受挫的自由基对催化。此外，红外光谱研究解释了阴离子的大小/电荷密度对溶剂化不敏感的阳离子 [TTBPyH] +和观察到的反应性的有趣影响。
• A mild and environmentally benign method for the synthesis of glycals in PEG-600/H2O
  作者：Jinzhong Zhao、Shanqiao Wei、Xiaofeng Ma、Huawu Shao

  DOI：10.1039/b821681a

  日期：——

  Glycals were synthesized via a simple, mild, convenient and environmentally benign procedure, in which protected glycosyl bromides undergo the reductive elimination in the presence of zinc in PEG-600/H2O at room temperature. The glycals were obtained in 75–92% isolated yields.

  糖醇通过一种简单、温和、方便且环保的程序合成，在该过程中，保护的糖苷溴化物在室温下与锌在PEG-600/H2O的存在下进行还原消除反应。糖醇的分离产率为75-92%。
• A Rapid Synthesis of Pyranoid Glycals Promoted by β-Cyclodextrin and Ultrasound
  作者：Jinzhong Zhao、Huawu Shao、Xin Wu、Shaojing Shi

  DOI：10.1002/cjoc.201180263

  日期：2011.7

  procedure for the synthesis of glycals from glycosyl bromides with very low zinc dust loading (1.5 equiv.) is described. The process is activated by β‐cyclodextrin and ultrasound. Based on 19 samples, this method has been demonstrated to be highly effective for a broad range of glycosyl bromides, including acid‐ or base‐sensitive and disaccharide glycosyl bromides. A yield of 85%–96% of glycals was obtained

  描述了一种从糖基溴化物中合成锌粉的负荷非常低（1.5当量）的便捷且环境友好的方法。β-环糊精和超声波可激活该过程。基于19个样品，该方法已被证明对多种糖基溴化物都非常有效，包括对酸或碱敏感的二糖基糖基溴化物。获得了85％–96％的缩醛收率。
• Improved synthesis of the Kijanimicin oligodeoxytetrasaccharide
  作者：Joachim Thiem、Henry Sajus

  DOI：10.1016/j.carres.2018.10.014

  日期：2019.1

  By sequential synthesis the four 2,6-dideoxy saccharide moieties of the kijanimicin tetrasaccharide could be stereoselectively assembled. For formation of all required 2-deoxy α-glycoside linkages various S-(hexopyranosyl)-phosphorodithioates as donor structures could be convincingly employed. The terminal 2-deoxy β-glycoside linkage was stereoselectively formed following the dibromomethyl methyl ether

  通过顺序合成奇异霉素四糖的四个2，6-二脱氧糖部分可以立体选择性地组装。为了形成所有需要的2-脱氧α-糖苷键，可以令人信服地采用各种S-（己基吡喃糖基）-二硫代磷酸酯作为供体结构。在二溴甲基甲基醚方法之后，立体选择性地形成了末端2-脱氧β-糖苷键。可以通过九个后续步骤以5％的总收率获得目标十八烷氧基-四糖-酰胺。