methyl 4,6-di-O-benzyl-α-D-glucopyranoside | 58341-71-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4,6-di-O-benzyl-α-D-glucopyranoside
• 英文别名: (2S,3R,4R,5S,6R)-2-methoxy-5-phenylmethoxy-6-(phenylmethoxymethyl)oxane-3,4-diol
• CAS: 58341-71-2
• 化学式: C₂₁H₂₆O₆
• 分子量: 374.434
• InChiKey: ITYFQCKIOPNCPG-ONUIULTDSA-N

物化性质

• 沸点：
  535.1±50.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4,6-di-O-benzyl-α-D-glucopyranoside 在 sodium hydroxide 、 sodium methylate 、 四丁基硫酸氢铵 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.33h， 生成 methyl 2,3-anhydro-4,6-di-O-benzyl-α-D-mannopyranoside
  参考文献：
  名称：

  Synthesis, crystalline structure, conformational analysis, and azidolysis of methyl 2,3-anhydro-α-d-manno- and -allo-pyranoside p-bromobenzyl

  摘要：

  Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-alpha-D-allopyranoside (6) was synthesized from methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (1) via the intermediate methyl 4,6-di-O-p-bromobenzyl-2,3-di-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Treatment of 6 with sodium azide selectively afforded methyl 3-azido-4,6-di-O-p-bromobenzyl-3-deoxy-alpha-D-glucopyranoside in 70% yield. Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-(17) and methyl 2,3-anhydro-4,6-di-O-benzyl-alpha-D-mannopyranoside (18) were obtained from 1 via the intermediates methyl 4,6-di-O-p-bromobenzyl- and methyl 4,6-di-O-benzyl-2-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Azidolysis of 17 and 18 with sodium azide in the presence of tetraethylammonium chloride in N,N-dimethylformamide gave the respective 3-azidoaltropyransides, in yields of 80%, by exclusive 3-attack. The crystal structure of compound 6 is orthorhombic with a space group of P2(1)2(1)2(1), and the 2,3-anhydropyranose moiety is in an almost ideal degrees-H-5 half-chair conformation. The crystals of 17 are also orthorhombic, belonging to space group P2(1)2(1)2(1), but the conformation is a hybrid of the degrees-H-5 half-chair and the degrees-E sofa. Analysis by NMR spectroscopy suggests that in solution in CDCl3 the conformation of 17 remains the same as, and that of 6 undergoes a change from, the respective solid-state conformations.

  DOI：

  10.1016/0008-6215(92)80086-g
• 作为产物：
  描述：

  O-ethyl-S-[(((methyl 3,4,6-tri-O-benzyl-α-D-glucopyranos-2-yl)dimethylsilyl)methyl)]dithiocarbonate 在 过氧化双月桂酰 、 溶剂黄146 、 四丁基氟化铵 作用下， 以 1,2-二氯乙烷 、 水 为溶剂， 反应 3.5h， 以81%的产率得到methyl 4,6-di-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  通过碳水化合物模板上的分子内氢原子转移实现无锡区域选择性自由基去氧苄基化。

  摘要：

  自由基选择性：苄基氢原子向O-甲硅烷基亚甲基的1,7-氢原子转移显着，引发了苄基化糖的区域选择性de- O-苄基化。该反应通过离子机理终止，并且通常用于具有多种官能团的羟基苄基化底物。

  DOI：

  10.1002/anie.201301783

文献信息

• <i>p</i>-Methylbenzyl Group: Oxidative Removal and Orthogonal Alcohol Deprotection
  作者：Kazutada Ikeuchi、Kentaro Murasawa、Kenya Ohara、Hidetoshi Yamada

  DOI：10.1021/acs.orglett.9b02144

  日期：2019.9.6

  describe the practical removal of p-methylbenzyl (MBn) protections of alcohols by treatment with 2,3-dichloro-5,6-dicyano-p-benzoquinone. When a molecule bears benzyl and MBn groups, the oxidant selectively removes the latter groups. Further, the MBn groups tolerate ceric ammonium nitrate, resulting in chemoselective removal of the p-methoxybenzyl group in the presence of the MBn groups. These orthogonal

  我们描述了通过用2,3-二氯-5,6-二氰基-对-苯醌处理来实际去除醇的对甲基苄基（MBn）保护。当一个分子带有苄基和MBn基团时，氧化剂会选择性地除去后者。此外，MBn基团耐受硝酸铈铈，导致在MBn基团存在下化学选择性除去对甲氧基苄基。这些正交的醇脱保护将提供有机化合物的新颖合成策略。
• A Facile Synthesis of Neosaccharides: 2,6′-and 3,6′-Ether-Linked Sugars
  作者：Shiro Ikegami、Hideyo Takahashi、Haruhiko Mitsuzuka、Kazusa Nishiyama

  DOI：10.1055/s-2006-926434

  日期：2006.5

  A novel synthesis of the 2,6′-O-linkage of methyl α-d-glucoside and methyl α-d-mannoside was developed based on an acetalization-reduction approach. Utilizing this approach, the 3,6′-O-linkage of methyl α-d-glucosides was also obtained. It is noteworthy that the reductive etherification of secondary alcohols and the C6-aldehyde of carbohydrates proceeded efficiently.

  基于乙缩醛化-还原方法，开发了一种新颖的甲基α-D-吡喃葡萄糖苷与甲基α-D-甘露糖苷之间的2,6′-O-连接合成。利用这种方法，还获得了甲基α-D-吡喃葡萄糖苷的3,6′-O-连接。值得注意的是，二级醇的还原醚化与碳水化合物的C6醛高效进行。
• A New Method for the Deprotection of Benzyl Ethers or the Selective Protection of Alcohols
  作者：Jacob Madsen、Christel Viuf、Mikael Bols

  DOI：10.1002/(sici)1521-3765(20000403)6:7<1140::aid-chem1140>3.3.co;2-y

  日期：2000.4.3

  A new selective method for the deprotection of benzyl ethers situated next to alcohols in the alpha, beta, or gamma position is presented which uses either NIS or DIB/I2 as a reagent. After initial formation of a hypoiodite intermediate, the reaction is believed to follow a radical pathway to resemble the Hoffman-Loffler-Freytag reaction. The formation of the intermediate hypoiodite is suggested on

  提出了一种新的选择性方法，该方法使用NIS或DIB / I2作为试剂，对位于α，β或gamma位置的醇旁边的苄基醚进行脱保护。最初形成次碘酸盐中间体后，该反应被认为遵循自由基途径，类似于霍夫曼-洛夫勒-弗莱塔格反应。在NMR研究的基础上，建议形成中间的次碘酸盐。取决于底物，分离出相应的亚苄基衍生物或二醇。
• A new synthesis of 2,3,4,6-tetra-O-benzyl-d-glucopyranosylidene acetals, using trimethylsilyl trifluoromethanesulfonate as the catalyst
  作者：Shigeomi Horito、Katsuji Asano、Kazuyuki Umemura、Hironobu Hashimoto、Juji Yoshimura

  DOI：10.1016/0008-6215(83)84015-4

  日期：1983.9

  in the presence of trimethylsilyl trifluoromethanesulfonate as the catalyst. Application to cis - and trans -1,2-diols containing primary, secondary, and tertiary hydroxyl groups was examined, and a new rearrangement was found in the reaction of a d -glucono-1,5-lactone derivative having an acetyl group at O-6.

  摘要在苯甲酸存在下，将2,3,4,6-四-O-苄基-d-葡萄糖酸-1,5-内酯与双-O-（三甲基甲硅烷基）-1,2-二醇缩合合成标题化合物。三甲基甲硅烷基三氟甲磺酸盐为催化剂。考察了对含伯，仲和叔羟基的顺式和反式-1,2-二醇的应用，并发现在O处具有乙酰基的ad -glucono-1,5-lactone衍生物的反应中发生了新的重排。 -6。
• Synthesis of a di- and a tri-saccharide related to the k-antigen of Klebsiella type 10 and a study of their inhibition in the precipitin reaction
  作者：Arun K. Sarkar、Asim K. Ray、Nirmolendu Roy

  DOI：10.1016/0008-6215(89)84124-2

  日期：1989.7

  Syntheses of methyl 3-O-alpha-D-galactopyranosyl-alpha-D-mannopyranoside (10) and methyl 3-O-alpha-D-galactopyranosyl-2-O-(beta-D-glucopyranosyluronic acid)-alpha-D-mannopyranoside (11) in good yield are described. Both 10 and 11 significantly inhibit antigen-antibody precipitation in the Klebsiella Type 10 immune system. The results provide more evidence for the structure (1) of the antigen from Klebsiella

  甲基3-O-α-D-吡喃半乳糖基-α-D-甘露吡喃糖苷（10）和甲基3-O-α-D-吡喃半乳糖基-2-O-（β-D-吡喃葡萄糖基糖醛酸）-α-D-描述了高产率的甘露吡喃糖苷（11）。10和11均显着抑制10型克雷伯菌免疫系统中的抗原抗体沉淀。该结果为来自克雷伯氏菌K-10的抗原的结构（1）及其免疫显性分组提供了更多的证据。