allyl 2,3,6-tri-O-benzyl-β-D-galactopyranoside | 150969-29-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl 2,3,6-tri-O-benzyl-β-D-galactopyranoside
• 英文别名: (2R,3S,4S,5R,6R)-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-prop-2-enoxyoxan-3-ol
• CAS: 150969-29-2
• 化学式: C₃₀H₃₄O₆
• 分子量: 490.596
• InChiKey: BBGJDOFVCMSOBF-HBMYTODVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  36
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  allyl 2,3,6-tri-O-benzyl-β-D-galactopyranoside 在 氢气 作用下， 以 乙醇 、 乙酸乙酯 为溶剂， 反应 3.0h， 以97.5%的产率得到propyl 2,3,6-tri-O-benzyl-β-D-galactopyranoside
  参考文献：
  名称：

  用唾液酸合成半乳糖上非天然键位的GM4异构体的化学方法。

  摘要：

  含有唾液酸的细胞表面聚糖参与多种生物学现象。但是，迄今尚未研究具有（2-> 2）和（2-> 4）键的GM4衍生物的合成。在这项研究中，对半乳糖上所有羟基的唾液酸化进行了研究，以合成GM4异构体。通过使用富含电子的苄基基团保护半乳糖基受体来实现区域选择性的唾液酸化。这些合成的唾液酸化聚糖将被证明是研究未知碳水化合物介导的生物学角色的有用工具。

  DOI：

  10.1016/j.carres.2014.10.018
• 作为产物：
  描述：

  allyl 2,3-di-O-benzyl-4,6-O-benzylidene-β-D-galactopyranoside 在 sodium cyanoborohydride 、 盐酸 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 1.5h， 以81.6%的产率得到allyl 2,3,6-tri-O-benzyl-β-D-galactopyranoside
  参考文献：
  名称：

  用唾液酸合成半乳糖上非天然键位的GM4异构体的化学方法。

  摘要：

  含有唾液酸的细胞表面聚糖参与多种生物学现象。但是，迄今尚未研究具有（2-> 2）和（2-> 4）键的GM4衍生物的合成。在这项研究中，对半乳糖上所有羟基的唾液酸化进行了研究，以合成GM4异构体。通过使用富含电子的苄基基团保护半乳糖基受体来实现区域选择性的唾液酸化。这些合成的唾液酸化聚糖将被证明是研究未知碳水化合物介导的生物学角色的有用工具。

  DOI：

  10.1016/j.carres.2014.10.018

文献信息

• An Easy and Versatile Approach for the Regioselective De-O-benzylation of Protected Sugars Based on the I2/Et3SiH Combined System
  作者：Antonello Pastore、Silvia Valerio、Matteo Adinolfi、Alfonso Iadonisi

  DOI：10.1002/chem.201003332

  日期：2011.5.16

  whereas the regioselectivity appears to be mainly controlled by steric effects. However, the presence of an electron withdrawing acyl protecting group can switch the regioselectivity to favour deprotection of the carbinol position farthest from the ester group. The protocol is experimentally simple and provides straightforward access in useful yields to a wide range of partially protected mono‐ and disaccharide

  使用便宜且易于处理的试剂，例如I 2和Et 3SiH在低温下可以从高度O-苄基化的碳水化合物中区域选择性地除去苄基保护基团。观察到的区域选择性取决于前体的性质，最难获得的甲醇经常被释放出来。机理研究表明，原位产生的HI是该过程的促进剂，而区域选择性似乎主要受空间效应控制。然而，吸电子酰基保护基的存在可以切换区域选择性，以促进最远离酯基的甲醇位置的脱保护。该协议在实验上很简单，可以以有用的收率直接访问各种部分受保护的单糖和二糖结构单元，这些单元对于合成生物学上有用的寡糖或高度官能化的手性化合物都具有重要意义。如此获得的部分受保护的糖也可以与糖基供体原位偶联，如从完全受保护的前体一锅法合成Lewis X模拟物所示。
• Synthesis of a model compound related to an anti-ulcer pectic polysaccharide
  作者：Michiko Maruyama、Tadahiro Takeda、Noriko Shimizu、Noriyasu Hada、Haruki Yamada

  DOI：10.1016/s0008-6215(99)00315-8

  日期：2000.4

  A stereocontrolled synthesis of the model compound for an anti-ulcer active polysaccharide (Bupleuran 2IIc) is described. Glycosidation of the disaccharide acceptor, 2-O-acetyl-3-O-benzyl-4-O-(p-methoxybenzyl)-alpha-L-rhamnopyranosyl-(1-- >4)-2,3,6-tri-O-benzyl-alpha-D-galactopyranosyl trichloroacetimidate, with the disaccharide receptor, allyl 3,4-di-O-benzyl-alpha-L-rhamnopyranosyl-(1-->4)-2,3,6-tri-O-benzyl-beta-

  描述了用于抗溃疡活性多糖（Bupleuran 2IIc）的模型化合物的立体控制合成。二糖受体2-O-乙酰基-3-O-苄基-4-O-（对甲氧基苄基）-α-L-鼠李糖基-（1--> 4）-2,3,6-tri-具有二糖受体的烯丙基3,4-二-O-苄基-α-L-鼠李糖基-（1-> 4）-2,3,6-tri-O用三氟甲磺酸银（AgOTf）作为促进剂的-苄基-β-D-吡喃半乳糖苷得到所需的四糖衍生物，将其转化为酸性四糖，对应于鼠李糖半乳糖醛酸聚糖（Bupleuran 2IIc）多糖的片段，丙基α-L- Rha-（1-> 4）-alpha-D-GalA-（1-> 2）-alpha-L-Rha-（1-> 4）-beta-D-GalA和酯保护基，然后氧化。
• Sialylation with systematically protected allyl galactoside acceptors using sialyl phosphate donors
  作者：Kenta Kurimoto、Hatsuo Yamamura、Atsushi Miyagawa

  DOI：10.1016/j.tetlet.2016.02.052

  日期：2016.3

  Various N-protected sialyl donors were synthesized and utilized in sialylation to investigate the reactivity and stereoselectivity of sialyl phosphate donors. Furthermore, in order to understand the effects of protecting groups and hydroxyl group positions on galactosyl acceptors, the sialylation efficiencies of all of the hydroxy groups on galactoses, which were protected with benzyl or benzoyl groups, were investigated. Consequently, the sialylation of N-acetyl-5-N,4-O-oxazolidinone-protected sialyl phosphate donors with allyl galactosides was accomplished and gave the GM4 regioisomers. (C) 2016 Elsevier Ltd. All rights reserved.
• Novel aspects of interaction between UDP-Gal and GlcNAc β-1,4-Galactosyltransferase: Transferability and remarkable inhibitory activity of UDP-(mono-O-methylated Gal), UDP-Fuc and UDP-Man
  作者：Tsuyoshi Endo、Yasuhiro Kajihara、Hisashi Kodama、Hironobu Hashimoto

  DOI：10.1016/s0968-0896(96)00176-9

  日期：1996.11

  Four mono-O-methylated and one mono-O-acetylated UDP-D-Gal analogues and UDP-L-Fuc were synthesized. 2-O-Methyl-D-galactose residue was enzymatically transferred to give 2'-O-methyIlactosaminide in high yield. UDP-Fuc and UDP-Man showed potent inhibitory activities against beta-1,4-galactosyltransferase. Structural requirement and steric allowance for the ground and transition states of the enzyme reaction were discussed. Copyright (C) 1996 Elsevier Science Ltd
• Synthesis of structural elements of the capsular polysaccharide of streptococcus pneumoniae type 8
  作者：Franciscus A.W. Koeman、Johannis P. Kamerling、Johannes F.G. Vliegenthart

  DOI：10.1016/s0040-4020(01)82378-4

  日期：1993.6

  The synthesis is reported of propyl 4-O-alpha-D-galactopyranosyl-beta-D-glucopyranosiduronic acid (25), 4-O-[4-O-(beta-D-glucopyranosyluronic acid)-beta-D-glucopyranosyl]-D-glucopyranose (34), and 4-O-(4-O-beta-D-glucopyranosyl-alpha-D-glucopyranosyl)-D-galactopyranose (38), each representing a structural element of the repeating unit of the capsular polysaccharide of Streptococcus pneumoniae type 8, [-->4)-beta-D-GlcpA-(1-->4)-beta-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Galp-(1-->]n. 2,3-Di-O-benzyl-4,6-O-benzylidene-alpha-D-galactopyranosyl trichloroacetimidate (12) was coupled to allyl 2-0-acetyl-3-O-benzyl-6-0-trityl-beta-D-glucopyranoside (7) in dichloromethane-ether, using trimethylsilyl trifluoromethanesulfonate as a promoter, to give disaccharide derivative 20. Detritylation of 20, followed by oxidation and deprotection, afforded disaccharide propyl glycoside 25. Coupling of 2,3,4,6-tetra-0-acetyl-alpha-D-glucopyranosyl trichloroacetimidate (8) to allyl 2,3,6-tri-O-benzyl-4-O-(2,3,6-tri-O-benzyl-beta-D-glucopyranosyl)-beta-D-glucopyranoside (17) in dichloromethane, with trimethylsilyl trifluoromethanesulfonate as a promoter, resulted in trisaccharide derivative 26. Deacetylation of 26, followed by 6-O-tritylation, benzylation, detritylation, and oxidation gave a protected trisaccharide derivative (31), which, after deprotection, afforded 34. Coupling of allyl 2,3,6-tri-O-benzyl-beta-D-galactopyranoside (10) to 4-O-(2,3-di-O-benzyl-4,6-O-benzylidene-beta-D-glucopyranosyl)-2,3,6-tri-O-benzyl-D-glucopyranosyl trichloroacetimidate (19) in ether, with trimethylsilyl trifluoromethanesulfonate as a promoter, gave trisaccharide derivative 35. Deallylation of 35, followed by hydrogenolysis afforded 38.