ethyl 3-O-benzyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside | 146608-95-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3-O-benzyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside
• 英文别名: ethyl 4,6-O-benzylidene-3-O-benzyl-1-thio-β-D-glucopyranoside；ethylthio 3-O-benzyl-4,6-O-benzylidene-β-D-glucopyranoside；Ethyl 3-O-benzyl-4,6-O-benzylidene-1-thio-beta-D-glucopyranoside；(4aR,6S,7R,8R,8aR)-6-ethylsulfanyl-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-ol
• CAS: 146608-95-9
• 化学式: C₂₂H₂₆O₅S
• 分子量: 402.511
• InChiKey: SYBHNKGJBUSZOA-NVZUTRPHSA-N

物化性质

• 沸点：
  576.7±50.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  82.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3-O-benzyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside 在 吡啶 作用下， 以 水 为溶剂， 反应 4.0h， 生成 ethyl 2-O-benzoyl-3-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  从新隐球菌血清D合成对应于胞外多糖重复单元的五糖。

  摘要：

  描述了来自新隐球菌血清D（即1）的胞外多糖的五糖重复单元的组装。1中的葡萄糖醛酸残基以吡喃葡萄糖苷的形式引入，并在合成的后期阶段被氧化。因此，在选择性去保护后，部分保护的甲基甘露吡喃糖苷11与乙硫基供体14的碘鎓离子辅助糖基化得到二糖18。后者与D-吡喃葡萄糖苷35的延伸得到三糖36。随后的保护基操作产生受体37。缩合。用三糖受体37制备二糖供体31得到五糖38。38的保护基操作得到42，其葡糖苷被氧化得到相应的葡糖醛酸苷44。44的加氢水解得到目标五糖1。

  DOI：

  10.1016/s0968-0896(96)00164-2
• 作为产物：
  描述：

  1,2,4,6-四-o-乙酰基-3-o-苄基-beta-d-吡喃葡萄糖 在 三氟化硼乙醚 、 sodium methylate 、 zinc(II) chloride 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 ethyl 3-O-benzyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Synthetic studies toward pyruvate acetal containing saccharides. Synthesis of the carbohydrate part of the Mycobacterium smegmatis pentasaccharide glycolipid and fragments thereof for the preparation of neoantigens

  摘要：

  A series of 2,3-di-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-D-glucopyranosyl donors (beta-phenylthio 3, bromide 4, alpha-chloride 5, beta-fluoride 6, and trichloroacetimidate 7) were prepared from the corresponding alpha-allyl glucoside 1 via the deallylated glucose 2 and were tested in glycosylation reactions with methanol to give the pyruvylated methyl glucosides 8 and 9 and with methyl 2,4,6-tri-O-benzoyl-beta-D-glucopyranoside 10 to give the disaccharide 11. Best results with respect to yield and beta-selectivity of the coupling were achieved with imidate 7. Thus, the 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-3-O-methyl-D-glucopyranosyl trichloroacetimidate 14 was prepared from its benzyl glucoside 12 and used for the synthesis of fragments related to the Mycobacterium smegmatis lipopentasaccharide. Trimethylsilyl trifluoromethanesulfonate-mediated condensation of 14, 5-[(benzyloxycarbonyl)amino]pentanol, and 10, respectively, followed by deblocking of the products 15 and 17 gave the pyruvylated aminopentyl glucoside 16 and methyl laminaribioside 18. Treatment of 17 with dichloromethyl methyl ether gave the laminaribiosyl chloride 19, coupling of which with protected 5-aminopentanol gave 20 also obtained from 14 and the monosaccharide nucleophile 26. The trisaccharide 5-aminopentyl glycoside fragment 42 was prepared by first coupling of 14 and benzyl 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-alpha-D-glucopyranoside 30 that was converted to the bispyruvylated laminaribiose imidate 33, followed by condensation with thioglycoside 38 obtainable in four steps from 1,2,4,6-tetra-O-acetyl-3-O-benzyl-beta-D-glucopyranose to give the trisaccharide ethyl thioglycoside 40. Next, NIS-mediated condensation of 40 and 5-[(benzyloxycarbonyl)amino]pentanol followed by deblocking gave 42. Pentasaccharide 45 was similarly prepared from 40 and hepta-O-benzoyltrehalose 43 to give first the blocked saccharide 44, deblocking of which afforded the target pentasaccharide.

  DOI：

  10.1021/jo00057a021

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。
• A 2,4-O-[(Z)-2-butenylene]-bridged glucopyranose: efficient construction of the bicyclic skeleton and its axial-rich twist-boat conformation
  作者：Yang Cao、Yusuke Kasai、Masafumi Bando、Mayumi Kawagoe、Hidetoshi Yamada

  DOI：10.1016/j.tet.2009.01.019

  日期：2009.3

  Synthesis and conformational analyses of 1-O-acetyl-3,6-di-O-benzyl-2,4-O-[(Z)-2-butenylene]-β-d-glucopyranose are described. The construction of the trioxabicyclo[6.3.1]dodecane skeleton of the compound was initiated from a ring-opened glucose, followed by the successive cyclization of first the nine-membered ring and then the six-membered ring. The pyranose of the compound was in 3S1, an axial-rich

  描述了1 - O-乙酰基-3，6-二-O-苄基-2，4- O -[（Z）-2-丁烯基]-β-d-吡喃葡萄糖的合成和构象分析。该化合物的三氧杂双环[6.3.1]十二烷骨架的构建是从开环的葡萄糖开始的，随后是先将九元环然后是六元环连续环化。该化合物的吡喃糖为3 S 1，一种富含轴向的扭转舟构象。该结果证明了与使用庞大的甲硅烷基保护基团的方法相比，用于将吡喃糖限制成富含轴向的扭转舟构象的替代方法。
• Synthesis of A Di-and a Trisaccharide Related to the Antigen from<i>Klebsiella</i>Type 43
  作者：Sumita Sarbajna、Anup K. Misra、Nirmolendu Roy

  DOI：10.1080/00397919808004824

  日期：1998.7

  Starting from D-galactose, D-mannose and D-glucose methyl alpha-D-galactopyranosyl-(1-->3)-alpha-D-mannopyranosyl-(1-->2)-alpha-D-mannopyranoside and allyl beta-D-mannopyranosyl-(1-->4)-beta-D-glucopyranosyl uronate were synthesised in a highly stereoselective manner.
• Synthesis of the Tetrasaccharide Repeating Unit of the Antigen from <i>Escherichia coli</i> O126 as Its Methyl Glycoside
  作者：Anup Kumar Misra、Nirmolendu Roy

  DOI：10.1080/07328309808001883

  日期：1998.9.1

  The tetrasaccharide repeating unit (17) of the antigen from E, coli O126 has been synthesized as its methyl glycoside by sequential addition of monosaccharide derivatives. The formation of the beta-mannosidic linkage was achieved by Swern oxidation of the glucose derivative followed by reduction of the product with sodium borohydride.
• Synthetic studies toward pyruvate acetal containing saccharides. Synthesis of the carbohydrate part of the Mycobacterium smegmatis pentasaccharide glycolipid and fragments thereof for the preparation of neoantigens
  作者：Thomas Ziegler、Elisabeth Eckhardt、Veronique Birault

  DOI：10.1021/jo00057a021

  日期：1993.2

  A series of 2,3-di-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-D-glucopyranosyl donors (beta-phenylthio 3, bromide 4, alpha-chloride 5, beta-fluoride 6, and trichloroacetimidate 7) were prepared from the corresponding alpha-allyl glucoside 1 via the deallylated glucose 2 and were tested in glycosylation reactions with methanol to give the pyruvylated methyl glucosides 8 and 9 and with methyl 2,4,6-tri-O-benzoyl-beta-D-glucopyranoside 10 to give the disaccharide 11. Best results with respect to yield and beta-selectivity of the coupling were achieved with imidate 7. Thus, the 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-3-O-methyl-D-glucopyranosyl trichloroacetimidate 14 was prepared from its benzyl glucoside 12 and used for the synthesis of fragments related to the Mycobacterium smegmatis lipopentasaccharide. Trimethylsilyl trifluoromethanesulfonate-mediated condensation of 14, 5-[(benzyloxycarbonyl)amino]pentanol, and 10, respectively, followed by deblocking of the products 15 and 17 gave the pyruvylated aminopentyl glucoside 16 and methyl laminaribioside 18. Treatment of 17 with dichloromethyl methyl ether gave the laminaribiosyl chloride 19, coupling of which with protected 5-aminopentanol gave 20 also obtained from 14 and the monosaccharide nucleophile 26. The trisaccharide 5-aminopentyl glycoside fragment 42 was prepared by first coupling of 14 and benzyl 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-alpha-D-glucopyranoside 30 that was converted to the bispyruvylated laminaribiose imidate 33, followed by condensation with thioglycoside 38 obtainable in four steps from 1,2,4,6-tetra-O-acetyl-3-O-benzyl-beta-D-glucopyranose to give the trisaccharide ethyl thioglycoside 40. Next, NIS-mediated condensation of 40 and 5-[(benzyloxycarbonyl)amino]pentanol followed by deblocking gave 42. Pentasaccharide 45 was similarly prepared from 40 and hepta-O-benzoyltrehalose 43 to give first the blocked saccharide 44, deblocking of which afforded the target pentasaccharide.