1-O-acetyl-2,3,4,6-tetra-O-benzyl-D-glucopyranoside | 56822-49-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-O-acetyl-2,3,4,6-tetra-O-benzyl-D-glucopyranoside
• 英文别名: (2R,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl acetate；1-O-acetyl-2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside；1-O-acetyl-2,3,4,6-tetra-O-benzyl-α-D-glucopyranose；acetyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside；[(2R,3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl] acetate
• CAS: 56822-49-2
• 化学式: C₃₆H₃₈O₇
• 分子量: 582.694
• InChiKey: YYFLBSFJOGQSRA-GJXDWMKPSA-N

物化性质

• 沸点：
  677.2±55.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  43
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-O-acetyl-2,3,4,6-tetra-O-benzyl-D-glucopyranoside 在 10percent Pd/C 三氟化硼乙醚 、 氢气 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 26.0h， 生成 (3R,5S)-3-((R)-13-Hydroxy-13-{(2R,5R,2'R,5'R)-5'-[(1S,5S)-5-hydroxy-1-((2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-hydroxymethyl-tetrahydro-pyran-2-yloxy)-undecyl]-octahydro-[2,2']bifuranyl-5-yl}-tridecyl)-5-methyl-dihydro-furan-2-one
  参考文献：
  名称：

  Synthesis, Spectroscopy, and Cytotoxicity of Glycosylated Acetogenin Derivatives as Promising Molecules for Cancer Therapy

  摘要：

  Several glycosyl derivatives of squamocin (1) have been synthesized by glycosylation under Lewis acid catalysis with two different 1-O-acetyl sugars. Separation of these compounds has been achieved by HPLC and centrifugal partition chromatography (CPC). A detailed NMR, ESIMS, and LSIMS study allowed complete structural elucidations. The cytotoxic activity of the glycosyl derivatives was investigated and compared with that of squamocin and drosquamocin against human epidermoid carcinoma cells (KB), African green monkey (Cercopithecus aethiops) kidney epithelial cells (VERO), and mouse lymphocytic leukemia cells (L1210). The antiproliferative effects of some derivatives were studied on cell cycles in mouse lymphocytic leukemia cells (L1210).

  DOI：

  10.1021/jm990568m
• 作为产物：
  描述：

  2,3,4,6-四苄基-D-吡喃葡萄糖 在 吡啶 、 碘代三甲硅烷 、 sodium acetate 、 四丁基硫酸氢铵 作用下， 以 二氯甲烷 为溶剂， 反应 6.08h， 生成 1-O-acetyl-2,3,4,6-tetra-O-benzyl-D-glucopyranoside
  参考文献：
  名称：

  Anionic Additions to Glycosyl Iodides:  Highly Stereoselective Syntheses of β C-, N-, and O-Glycosides¹

  摘要：

  Classically, glycosyl halides are activated as glycosyl donors by metal chelation under Koenigs-Knorr or Helferich conditions. These reactions often proceed through oxonium formation, and the stereochemical outcome is dictated by the anomeric effect and/or the nature of the protecting group on the C2 hydroxyl. Alternatively, glycosyl halides may undergo direct displacement of the halide by an incoming nucleophile in an S(N)2 mechanism. The latter reaction is far less common, and before this study it was primarily performed with glycosyl bromides. Having recently shown that both alpha and beta glycosyl iodides could be efficiently generated, we embarked upon an investigation of nucleophilic additions to glycosyl iodides. The studies reported herein show that additions of stabilized anions to alpha-glycosyl iodides proceed with inversion of stereochemistry to give beta-glycosides, even in the absence of a C2 participatory group. Glucosyl, galactosyl, and mannosyl iodides were studied, and the combined results indicate that the reactivity of 2,3,4,6-tetra-O-benzyl-alpha-D-galactosyl iodide > 2,3,4,6-tetra-O-benzyl-alpha-D-glucosyl iodide > 2,3,4,6-tetra-O-benzyl-alpha-D-mannosyl iodide. Both the glucosyl and galactosyl iodides are susceptible to E-2 elimination when treated with highly basic anions. In contrast, the mannosyl iodide undergoes substitution to give the 1,2 cis configuration. The overall sequence involves reaction of an anomeric acetate with trimethylsilyl iodide with in vacuo removal of the resulting trimethylsilyl acetate. The iodide is then treated with a nucleophile without further characterization. A variety of nucleophiles were stereoselectively added to the glycosyl halides providing beta-, C-, N-, and O-glycosides.

  DOI：

  10.1021/jo970922t

文献信息

• Improved preparation of 4(5)-aryl-2-(β-<scp>d</scp>-glucopyranosyl)-imidazoles, the most efficient glucose analogue inhibitors of glycogen phosphorylase
  作者：Eszter Szennyes、Éva Bokor、Gyula Batta、Tibor Docsa、Pál Gergely、László Somsák

  DOI：10.1039/c6ra21839c

  日期：——

  currently most efficient glucose derived inhibitors of glycogen phosphorylase enzymes was amended and extended by using O-perbenzylated β-D-glucopyranosyl cyanide as the starting material. This compound and its derivatives C-(β-D-glucopyranosyl)formimidate and formamidine were obtained in large scale reactions to give the products in ∼20 grams amounts. Ring closing reactions of the formimidate and formamidine

  通过使用O-过苄基化的β- D-吡喃葡萄糖基氰化物作为邻苯二甲酸酯，对目前最有效的葡萄糖衍生的糖原磷酸化酶抑制剂的4（5）-芳基-2-（β- D-吡喃葡萄糖基）-咪唑的合成进行了改进和扩展。起始材料。通过大规模反应获得了该化合物及其衍生物C-（β- D-吡喃葡萄糖基）甲酸酯和甲am，得到的产物约为20克。甲亚氨酸和甲am分别通过α-氨基和α-溴代酮的闭环反应产生了O-过苄基化的咪唑，其通过催化氢化或通过EtSH / BF 3 ·OEt 2脱保护。。新制备的4（5） - （4-硝基-和氨基苯基）-2-（β- d吡喃葡萄糖基） -咪唑证明效率较低的抑制剂（ķ我值分别为1141和411纳米，）比它们的未取代的对应物（ķ i = 280 nM）。
• [EN] MANNOSE DERIVATIVES FOR TREATING BACTERIAL INFECTIONS<br/>[FR] DÉRIVÉS DE MANNOSE POUR LE TRAITEMENT D'INFECTIONS BACTÉRIENNES
  申请人：VERTEX PHARMA

  公开号：WO2014100158A1

  公开（公告）日：2014-06-26

  The present invention relates to compounds useful for the treatment or prevention of bacteria infections. These compounds have formula (I). The invention also provides pharmaceutically acceptable compositions containing the compounds and methods of using the compositions in the treatment of bacteria infections. Finally, the invention provides processes for making compounds of the invention.

  本发明涉及用于治疗或预防细菌感染的化合物。这些化合物具有化学式（I）。该发明还提供含有这些化合物的药学上可接受的组合物，以及使用这些组合物治疗细菌感染的方法。最后，该发明提供了制备本发明化合物的方法。
• Establishment of Guidelines for the Control of Glycosylation Reactions and Intermediates by Quantitative Assessment of Reactivity
  作者：Chun‐Wei Chang、Chia‐Hui Wu、Mei‐Huei Lin、Pin‐Hsuan Liao、Chun‐Chi Chang、Hsiao‐Han Chuang、Su‐Ching Lin、Sarah Lam、Ved Prakash Verma、Chao‐Ping Hsu、Cheng‐Chung Wang

  DOI：10.1002/anie.201906297

  日期：2019.11.18

  Stereocontrolled chemical glycosylation remains a major challenge despite vast efforts reported over many decades and so far still mainly relies on trial and error. Now it is shown that the relative reactivity value (RRV) of thioglycosides is an indicator for revealing stereoselectivities according to four types of acceptors. Mechanistic studies show that the reaction is dominated by two distinct intermediates:

  尽管数十年来进行了大量的努力，但立体控制的化学糖基化仍然是一个主要挑战，到目前为止，仍然主要依靠反复试验。现在表明，硫糖苷的相对反应性值（RRV）是根据四种受体揭示立体选择性的指标。机理研究表明，该反应由两种不同的中间体控制：糖基三氟甲磺酸酯和来自N-卤代琥珀酰亚胺（NXS）/ TfOH的糖基卤化物。糖基卤化物的形成与α-糖苷的产生高度相关。这些发现使得能够通过使用RRV作为α/β-选择性指示剂来预见糖基化反应，并且为立体控制糖基化开发了指导方针和规则。
• Chemoselective and Diastereoselective Synthesis of <i>C</i> ‐Aryl Nucleoside Analogues by Nickel‐Catalyzed Cross‐Coupling of Furanosyl Acetates with Aryl Iodides
  作者：Yuxi Li、Zheng Wang、Luyang Li、Xiaoying Tian、Feng Shao、Chao Li

  DOI：10.1002/anie.202110391

  日期：2022.1.3

  The facile synthesis of C-aryl nucleoside analogues from readily available furanose acetates and aryl iodides is disclosed. This nickel-catalyzed cross-electrophile coupling showed good functional-group compatibility and excellent β-selectivity. The high chemoselectivity with respect to aryl iodides enabled the efficient preparation of a variety of C-aryl halide furanosides suitable for various po

  公开了从容易获得的呋喃糖乙酸酯和芳基碘化物轻松合成C-芳基核苷类似物。这种镍催化的交叉亲电偶联表现出良好的官能团相容性和优异的β-选择性。对芳基碘化物的高化学选择性使得能够有效制备适用于各种后官能化反应的各种C-芳基卤化物呋喃糖苷。
• SIMPLE SYNTHESIS OF GLYCOSYL FLUORIDES
  作者：Masahiko Hayashi、Shun-ichi Hashimoto、Ryoji Noyori

  DOI：10.1246/cl.1984.1747

  日期：1984.10.5

  Treatment of 1-unprotected or -O-acetylated sugar derivatives with a hydrogen fluoride–pyridine mixture affords the corresponding 1-fluoro derivatives in high yields.

  以氢氟化-吡啶混合液处理未保护或O-乙酰化的糖衍生物，可以高产率地得到相应的1-氟代衍生物。