p-methoxyphenyl 2,4,6-tri-O-acetyl-β-D-galactopyranoside | 383905-62-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-methoxyphenyl 2,4,6-tri-O-acetyl-β-D-galactopyranoside
• 英文别名: 4-methoxyphenyl 2,4,6-tri-O-acetyl-β-D-galactopyranoside；4-Methoxyphenyl 2,4,6-tri-O-acetyl-b-D-galactopyranoside；[(2R,3R,4S,5R,6S)-3,5-diacetyloxy-4-hydroxy-6-(4-methoxyphenoxy)oxan-2-yl]methyl acetate
• CAS: 383905-62-2
• 化学式: C₁₉H₂₄O₁₀
• 分子量: 412.394
• InChiKey: MTBKQQXLXHXGKW-ICBNADEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  127
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  p-methoxyphenyl 2,4,6-tri-O-acetyl-β-D-galactopyranoside 在 molecular sieve 、 ammonium cerium(IV) nitrate 、 三氟甲磺酸三甲基硅酯 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醚 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 9.5h， 生成 3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-2,4,6-tri-O-acetyl-α-D-galactopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Synthesis of a divalent glycoside of an α-galactosyl disaccharide epitope involved in the hyperacute rejection of xenotransplantation

  摘要：

  3,6-Dioxaoct-1,8-diyl di-(3-O-alpha -D-galactopyranosyl-beta -D-galactopyranoside) was synthesized for use in research on hyperacute rejection of xeno transplantation. The trichloroacetate method was successfully applied to form stereoselectively the a-D-galactosyl linkage under mild reaction conditions and a simple procedure. The divalent O-glycoside was formed from the corresponding trichloroacetimidate in one step with reasonable yield. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00194-x
• 作为产物：
  描述：

  4-methoxyphenyl 2,4,6-tri-O-acetyl-3-O-allyl-β-D-galactopyranoside 在 palladium dichloride 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 3.5h， 以69%的产率得到p-methoxyphenyl 2,4,6-tri-O-acetyl-β-D-galactopyranoside
  参考文献：
  名称：

  2，6-二取代的2- O-苯甲酰基在糖基化反应中的相邻基团参与：机理研究

  摘要：

  对于NIS / TfOH介导的4-甲氧基苯基2,4,6-四-O-乙酰基-β-D-吡喃半乳糖苷和带有乙酰基，苯甲酰基，2,6-二甲氧基苯甲酰基的硫代半乳糖苷的反应，获得了不同的收率和糖基化立体选择性。在2-位的是2,4,6-三甲基苯甲酰基或2,6-二氯苯甲酰基，其余为乙酰基。4-甲基苯基2,3,4,6-四的X射线结构Ö - （2,4,6-三甲基苯甲酰）-1-硫代β-d-galactopyr anoside和4-甲基苯基3,4- ø -异亚丙基-2,6-二-O-（2,4,6-三甲基苯甲酰基）-1-硫代-β-D-吡喃半乳糖苷显示轻微扭曲的4 C 1椅子构象。可变温度NMR显示4-甲基苯基2,3,4,6-tetra- O的活化-（2,4,6-三甲基苯甲酰基）-1-硫代-β-D-吡喃半乳糖苷仅提供二恶唑鎓离子，而4-甲基苯基3,4,6-三-O-乙酰基-2- O-（2,4， 6-三甲基苯甲酰基）-1-

  DOI：

  10.1080/07328303.2010.508141

文献信息

• 2,6-Disubstituted Benzoates As Neighboring Groups for Enhanced Diastereoselectivity in β-Galactosylation Reactions: Synthesis of β-1,3-Linked Oligogalactosides Related to Arabinogalactan Proteins
  作者：Nathan W. McGill、Spencer J. Williams

  DOI：10.1021/jo902100q

  日期：2009.12.18

  plagued with poor stereoselectivity and side reactions including orthoester formation and transesterification of the 2-O-acyl group from the donor to the acceptor. We have investigated the use of 2,6-disubstituted benzoyl groups as bulky neighboring groups on the glycosyl donor. A 2,4,6-trimethylbenzoyl group was found to be optimal and enabled the formation of the β-galactopyranose-1,3-β-galactopyranose

  阿拉伯半乳聚糖蛋白（AGP）是植物糖蛋白，含有β-1,3-连接的半乳​​聚糖核心。使用各种2 - O-酰基保护的糖基供体合成β-吡喃半乳糖-1,3-β-吡喃半乳糖键一直困扰着不良的立体选择性和副反应，包括原酸酯形成和2- O的酯交换反应-从供体到受体的酰基。我们已经研究了使用2，6-二取代的苯甲酰基作为糖基供体上的大体积邻近基团。发现2,4,6-三甲基苯甲酰基是最佳的，能够形成与已解除武装的酯保护的受体的β-半乳糖吡喃糖-1,3-β-半乳糖吡喃糖键，抑制酯交换反应并减少原酸酯的形成，同时增强β-半乳糖基化反应的选择性。制备了一系列β-1,3-连接的寡半乳糖苷，并精制为新糖缀合物，用于研究AGP的生物合成和AGP结合蛋白。
• Remarkable Solvent Effect on Pd(0)-Catalyzed Deprotection of Allyl Ethers Using Barbituric Acid Derivatives: Application to Selective and Successive Removal of Allyl, Methallyl, and Prenyl Ethers
  作者：Hirokazu Tsukamoto、Takamichi Suzuki、Yoshinori Kondo

  DOI：10.1055/s-2007-992352

  日期：——

  Pd(0)-catalyzed deprotection of allyl ethers using barbituric acid derivatives in protic polar solvent such as MeOH and aqueous 1,4-dioxane proceeds at room temperature without affecting a wide variety of functional groups. Control of the reaction temperature allows selective and successive cleavage of allyl, methallyl, and prenyl ethers. A study of ligand effects on the deprotection reveals that the

  使用巴比妥酸衍生物在质子极性溶剂（如 MeOH 和 1,4-二恶烷水溶液中）中 Pd(0) 催化的烯丙基醚脱保护在室温下进行，而不会影响多种官能团。反应温度的控制允许烯丙基、甲代烯丙基和异戊二烯醚的选择性和连续裂解。配体对脱保护作用的研究表明，甲醇中反应性的提高是由于加速氧化加成到 Pd(0)。
• Stereodirecting Effect of C5-Carboxylate Substituents on the Glycosylation Stereochemistry of 3-Deoxy-<scp>d</scp>-<i>manno</i>-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of α- and β-Kdo Glycosides
  作者：Wei Huang、Ying-Yu Zhou、Xing-Ling Pan、Xian-Yang Zhou、Jin-Cai Lei、Dong-Mei Liu、Yue Chu、Jin-Song Yang

  DOI：10.1021/jacs.7b09461

  日期：2018.3.14

  manno-oct-2-ulosonic acid (Kdo) ethyl thioglycoside donors is presented. The coupling of 5- O-arylcarbonyl or acetyl protected Kdo thioglycosides with acceptors proceeds in an α-selective and high-yielding manner, leading to formation of α-linked Kdo glycosides products. On the other hand, the glycosylation stereoselectivity of the 5- O-2-quinolinecarbonyl (Quin) or 4-nitropicoloyl substituted Kdo thioglycoside

  介绍了 C5-酯功能对 3-脱氧-d-甘露糖-oct-2-ulosonic 酸 (Kdo) 乙基硫糖苷供体的糖基化立体选择性的立体定向作用。5-O-芳基羰基或乙酰基保护的 Kdo 硫糖苷与受体的偶联以α-选择性和高产率的方式进行，导致形成 α-连接的 Kdo 糖苷产物。另一方面，5-O-2-喹啉羰基 (Quin) 或 4-硝基吡啶甲酰基取代的 Kdo 硫糖苷供体的糖基化立体选择性是可切换的：(1) 带有主要糖基受体的 Kdo 供体的 5-O-Quin 的糖基化显示出完全的 β-立体选择性，以良好到极好的收率提供相应的 β-糖苷。(2) 具有这些 Kdo 供体的二级受体的立体化学结果主要取决于受体的立体电子性质。当 Kdo 供体与解除武装或高度拥挤的二级碳水化合物受体偶联时，仅获得或主要获得 α 异头产物，而选择性可能会在携带 5-O-4-硝基吡啶甲酰基的供体与更具反应性的仲醇的糖基化中转变为主要的
• α-Selective synthesis of 2-deoxy-glycosides and disaccharides
  作者：Guofang Yang、Xiaosheng Luo、Hong Guo、Qingbing Wang、Jiafen Zhou、Tianyun Huang、Jie Tang、Junjie Shan、Jianbo Zhang

  DOI：10.1080/07328303.2018.1439498

  日期：2018.3.24

  A metal-free catalytic method for the synthesis of 2-deoxy glycosides and disaccharides has been developed using stable 2-deoxy glucosyl and galactosyl acetate donors. They could react with a variety of acceptors in the presence of catalytic amount of TMSOTf at 0 degrees C to form glycosides, glycoconjugates, and disaccharides with excellent alpha-selectivity (> 19:1) and yields (up to 99%) in a short time (0.5 h). With this expedient method, several new compounds against human K562 and SMMC7721 cell lines were obtained and tested with in vitro antitumor bioactivities.
• Synthesis of the glycosaminoglycan–protein linkage tetraosyl peptide moieties of betaglycan, which serve as a hexosamine acceptor for enzymatic glycosyl transfer
  作者：Jun-ichi Tamura、Tomomi Nakamura-Yamamoto、Yuko Nishimura、Shuji Mizumoto、Jun Takahashi、Kazuyuki Sugahara

  DOI：10.1016/j.carres.2010.06.019

  日期：2010.10

  Betaglycan, also known as TGF-beta type III receptor, is a membrane-anchored proteoglycan, which has two glycosaminoglycan (GAG) attachment sites (Lopez-Casillas, F.; Payne, H. M.; Andres, J. L.; Massague, J. J. Cell Biol. 1994, 124, 557-568). Chondroitin sulfate (CS) or heparan sulfate (HS) can attach to the first site, Ser(535), whereas only CS attaches to the second, Ser(546). Although the mechanism behind the assembly of CS and HS is not fully understood, it has been reported that the assembly of HS requires not only a cluster of acidic residues but also hydrophobic residues located near the Ser-Gly attachment sites (Esko, J. D. Zhang, L Curr. Opin. Struct. Biol. 1996, 6, 663-670). To further understand the effects of amino acids close to the Ser residues of the GAG-attachment sites on the glycosyltransferases, two tetraosyl peptides derived from the CS attachment sites of betaglycan, GLcA-Gal-Gal-Xyl-SerGlyAspAsnGly (1) and GLcA-Gal-Gal-Xyl-SerGlyAspAsnGlyPheProGly (2), were synthesized, and used as donor substrates for beta 1,4-N-acetylgalactosaminyltransferase-I (alpha 4GaINAcT-I) and alpha 1,4-N-acetylglucosaminyltransferase-I (beta 4GlcNAcT-I). Both the chemically synthesized linkage region tetrasaccharides were far better acceptors for beta 4GalNAcT-I than for alpha 4GlcNAcT-1 in vitro, although they also showed appreciable acceptor activity for alpha 4GlcNAcT-I. (C) 2010 Elsevier Ltd. All rights reserved.