ethyl 6-O-benzoyl-2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside | 195192-50-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 6-O-benzoyl-2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside
• CAS: 195192-50-8
• 化学式: C₃₆H₃₈O₆S
• 分子量: 598.76
• InChiKey: CLTMEGSIFDAOOL-QOKMRYHPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.08
• 重原子数：
  43.0
• 可旋转键数：
  14.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  63.22
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  ethyl 6-O-benzoyl-2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 四丁基溴化铵 、 溴 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 0.25h， 生成 methyl 6-O-benzoyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  Glycosidation of Thioglycosides in the Presence of Bromine: Mechanism, Reactivity, and Stereoselectivity

  摘要：

  Elaborating on previous studies by Lemieux for highly reactive "armed" bromides, we discovered that beta-bromide of the superdisarmed (2-O-benzyl-3,4,6-tri-O-benzoyl) series can be directly obtained from the thioglycoside precursor. When this bromide is glycosidated, alpha-glycosides form exclusively; however, the yields of such transformations may be low due to the competing anomerization into alpha-bromide that is totally unreactive under the established reaction conditions.

  DOI：

  10.1021/jo2019174
• 作为产物：
  描述：

  ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside 、 苯甲酰氯 以 吡啶 为溶剂， 反应 1.0h， 以90%的产率得到ethyl 6-O-benzoyl-2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Van Strafen; Kriek; Timmers, Journal of Carbohydrate Chemistry, 1997, vol. 16, # 6, p. 947 - 966

  摘要：

  DOI：

文献信息

• Convenient construction of a variety of glycosidic linkages using a universal glucosyl donor
  作者：Ken-ichi Sato、Shoji Akai、Koudai Sakai、Masaru Kojima、Hideshige Murakami、Tetsuya Idoji

  DOI：10.1016/j.tetlet.2005.08.109

  日期：2005.10

  The donor 8 undergoes glycosidation with a primary carbohydrate alcohol 7 to give disaccharide 9 having a 1,2-cis-α-glycosidic linkage in 90% yield. The construction of the corresponding 1,2-trans-α-glycosidic linkage was performed in 68% yield (three steps) from 9. A similar glycosidation of the 2-O-(N-phenylcarbamoyl)-glucosyl donor 6 derived from 8 with 7 gave disaccharide 11 having a 1,2-trans-β-glycosidic

  这封信涉及使用通用的葡萄糖基供体构建糖苷键的四种类型（顺式-α，反式-α，顺式-β和反式-β）的概念。由d-葡萄糖以36％的产率合成选择性保护的通用葡萄糖基供体8（八步）。供体8用伯糖醇7进行糖基化，以90％的产率得到具有1，2-顺式-α-糖苷键的二糖9。相应的1,2-反式-α-糖苷键的构建以68％的收率（三个步骤）从9进行。由8衍生的2- O-（N-苯基氨基甲酰基）-葡萄糖基供体6与7的类似糖苷化以75％的产率得到具有1,2-反式-β-糖苷键的二糖11。从11开始，相应的1,2-顺式-β-连接的构建以53％的产率（三个步骤）进行。
• 1,2-<i>trans</i> Glycosylation via Neighboring Group Participation of 2-<i>O</i>-Alkoxymethyl Groups: Application to One-Pot Oligosaccharide Synthesis
  作者：Milandip Karak、Yohei Joh、Masahiko Suenaga、Tohru Oishi、Kohei Torikai

  DOI：10.1021/acs.orglett.9b00220

  日期：2019.2.15

  The use of 2-O-alkoxymethyl groups as effective stereodirecting substituents for the construction of 1,2-trans glycosidic linkages is reported. The observed stereoselectivity arises from the intramolecular formation of a five-membered cyclic architecture between the 2-O-alkoxymethyl substituent and the oxocarbenium ion, which provides the expected facial selectivity. Furthermore, the observed stereocontrol

  据报道，使用2- O-烷氧基甲基作为有效的立体定向取代基来构建1，2-反式糖苷键。观察到的立体选择性来自2- O-烷氧基甲基取代基和氧碳鎓离子之间的五元环状结构的分子内形成，这提供了预期的面部选择性。此外，观察到的立体控制和2 - O-烷氧基甲基保护的供体的极高反应性允许开发一锅顺序糖基化策略，该策略应成为组装寡糖的有力工具。
• Synthesis of a common trisaccharide fragment of glycoforms of the outer core region of the Pseudomonas aeruginosa lipopolysaccharide
  作者：Bozhena S. Komarova、Yury E. Tsvetkov、Yuriy A. Knirel、Ulrich Zähringer、Gerald B. Pier、Nikolay E. Nifantiev

  DOI：10.1016/j.tetlet.2006.03.045

  日期：2006.5

  β-glucosylation of an α-(1→4)-linked Glc-GalN3 unit, did not lead to the target trisaccharide backbone. Further O-deacetylation, azido group reduction and debenzylation of the protected trisaccharide precursor gave the corresponding trisaccharide amine. The latter structure was used in the synthesis of a series of trisaccharides bearing an acetyl group, an l-alanine or an N-acetylated l-alanine residue

  报道了铜绿假单胞菌脂多糖外核心区糖型的常见三糖的首次合成。通过对β-（1→3）连接的6 - O-苄基-2-叠氮基-2-脱氧-3 - O -（- ）进行高效的α-（1→4）-葡萄糖基化反应，可以制备出具有完全保护作用的三糖前体。2,3,4,6-四-O-乙酰基-β-d-吡喃葡萄糖基）-α-d-吡喃半乳糖苷。相反，糖基化的替代序列涉及与α-（1→4）连接的Glc-GalN 3的β-糖基化单位，没有导致目标三糖骨架。被保护的三糖前体的进一步O-脱乙酰基，叠氮基还原和脱苄基反应得到相应的三糖胺。后一种结构用于合成一系列三糖，其在GalN的C-2的氨基上带有乙酰基，1-丙氨酸或N-乙酰化的1-丙氨酸残基。
• Halobenzoyl groups in glycosylation: effect on stereoselectivity and reactivity of glycosyl donors
  作者：S. Visansirikul、J. P. Yasomanee、A. V. Demchenko

  DOI：10.1007/s11172-015-0987-2

  日期：2015.5

  Described herein is the synthesis and evaluation of a series of glycosyl donors equipped with halobenzoyl substituents at O(4) and O(6) to study their properties in glycosylations. Among possible effects that may include carbonyl participation or H-bond mediated aglycone delivery, our results indicate that halobenzoyls act via a different mode.

  本文描述的是一系列在 O(4) 和 O(6) 处配备卤代苯甲酰基取代基的糖基供体的合成和评估，以研究它们在糖基化中的特性。在可能包括羰基参与或 H 键介导的苷元传递的可能影响中，我们的结果表明卤代苯甲酰基通过不同的模式起作用。
• A Useful and Convenient Synthetic Procedure for Hydrolysis of Thioglycosides
  作者：Ejabul Mondal、Pankaj M. Bujar Barua、Gopal Bose、Abu T. Khan

  DOI：10.1246/cl.2002.210

  日期：2002.2

  Various thioglycosides 1 are smoothly hydrolyzed chemoselectively to the corresponding 1-hydroxy sugars 2 in good yields at 0–5 °C by employing (NH4)6Mo7O24·4H2O-H2O2 or H2MoO4·H2O-H2O2 to promote oxidation of ammonium bromide in the presence of perchloric acid in CH2Cl2-H2O solvent system. Mild conditions, good yields, no side reactions such as bromination either at the anomeric position or double

  通过使用 (NH4)6Mo7O24·4 -H2O2 或 H2MoO4·H2O- 促进溴化铵在CH2Cl2- 溶剂体系中的高氯酸。温和的条件、良好的收率、在异头位置或双键处无副反应（如溴化），甚至在硫处氧化是一些主要优点。