p-methoxyphenyl 6-O-benzoyl-2,4-di-O-benzyl-β-D-glucopyranoside | 1541178-80-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-methoxyphenyl 6-O-benzoyl-2,4-di-O-benzyl-β-D-glucopyranoside
• CAS: 1541178-80-6
• 化学式: C₃₄H₃₄O₈
• 分子量: 570.639
• InChiKey: CNZONOJTLKEWSI-RFLLRRRSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.19
• 重原子数：
  42.0
• 可旋转键数：
  12.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  92.68
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  p-methoxyphenyl 6-O-benzoyl-2,4-di-O-benzyl-β-D-glucopyranoside 、 乙酰丙酸 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以96%的产率得到p-methoxyphenyl 6-O-benzoyl-2,4-di-O-benzyl-3-O-levulinoyl-β-D-glucopyranoside
  参考文献：
  名称：

  五糖和真菌α-（1→3）-葡聚糖相关的新糖缀合物的合成及其在烟曲霉细胞壁抗体制备中的应用

  摘要：

  烟曲霉细胞壁的α-（1→3）-葡聚糖片段3-氨基丙基α-（1→3）-五葡糖苷是通过块状方法合成的。带有立体定向6- O-苯甲酰基的单糖和二糖N-苯基三氟乙酰亚氨酸盐的应用对于立体选择性α-葡萄糖基化至关重要。在产品中，p‐甲氧基苯基和乙酰丙酰基分别用作异头位置和3-OH基团的正交保护基。它们从共有的嵌段中除去导致供体和受体被用于合成五糖。游离的α-（1→3）-五葡糖苷与生物素和牛血清白蛋白（BSA）的偶联为糖基结合物的真菌学研究提供了工具。用BSA偶联物免疫小鼠会诱导产生识别烟曲霉细胞壁上的α-（1→3）-葡聚糖的抗体，并区分其形态型。这一发现代表了诊断测试系统和疫苗的开发的第一步，该系统可以检测和抵抗这种威胁生命的病原体。

  DOI：

  10.1002/chem.201404770
• 作为产物：
  描述：

  苯甲酰氯 在 吡啶 、 硼烷四氢呋喃络合物 、 三氟甲磺酸三甲基硅酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 p-methoxyphenyl 6-O-benzoyl-2,4-di-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  Is an acyl group at O-3 in glucosyl donors able to control α-stereoselectivity of glycosylation? The role of conformational mobility and the protecting group at O-6

  摘要：

  The stereodirecting effect of a 3-O-acetyl protecting group, which is potentially capable of the remote anchimeric participation, and other protecting groups in 2-O-benzyl glucosyl donors with flexible and rigid conformations has been investigated. To this aim, an array of N-phenyltrifluoroacetimidoyl and sulfoxide donors bearing either 3-O-acetyl or 3-O-benzyl groups in combination with 4,6-di-O-benzyl, 6-O-acyl-4-O-benzyl, or 4,6-O-benzylidene protecting groups was prepared. The conformationally flexible 3-O-acetylated glucosyl donor protected at other positions with O-benzyl groups demonstrated very low or no alpha-stereoselectivity upon glycosylation of primary or secondary acceptors. On the contrary, 3,6-di-O-acylated glucosyl donors proved to be highly alpha-stereoselective as well as the donor having a single potentially participating acetyl group at O-6. The 3,6-di-O-acylated donor was shown to be the best alpha-glucosylating block for the primary acceptor, whereas the best alpha-selectivity of glycosylation of the secondary acceptor was achieved with the 6-O-acylated donor. Glycosylation of the secondary acceptor with the conformationally constrained 3-O-acetyl-4,6-O-benzylidene-protected donor displayed under standard conditions (-35 degrees C) even lower alpha-selectivity as compared to the 3-O-benzyl analogue. However, increasing the reaction temperature essentially raised the alpha-stereoselectivities of glycosylation with both 3-O-acetyl and 3-O-benzyl donors and made them almost equal. The stereodirecting effects of protecting groups observed for N-phenyltrifluoroacetimidoyl donors were also generally proven for sulfoxide donors. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2013.11.016

文献信息

• Combination of 3-<i>O</i>-Levulinoyl and 6-<i>O</i>-Trifluorobenzoyl Groups Ensures α-Selectivity in Glucosylations: Synthesis of the Oligosaccharides Related to <i>Aspergillus fumigatus</i> α-(1 → 3)-<scp>d</scp>-Glucan
  作者：Bozhena S. Komarova、Natalia S. Novikova、Alexey G. Gerbst、Olga A. Sinitsyna、Ekaterina A. Rubtsova、Elena G. Kondratyeva、Arkady P. Sinitsyn、Nikolay E. Nifantiev

  DOI：10.1021/acs.joc.3c01283

  日期：2023.9.1

  conformational nature and confirmed by DFT calculations. The potential of this donor, as well as the orthogonality of TFB and Lev protecting groups, is showcased by the synthesis of α-(1 → 3)-linked pentaglucoside corresponding to Aspergillus fumigatus α-(1 → 3)-d-glucan and of its hexasaccharide derivative, bearing β-glucosamine residue at the non-reducing end.

  使用葡萄糖基N-苯基三氟乙酰亚胺酯 (PTFAI) 供体在 O-6 处用吸电子 2,4,5-三氟苯甲酰基 (TFB) 基团进行保护，从而实现碳水化合物受体上伯羟基和仲羟基的立体特异性 α-葡萄糖基化，并且O-3 处参与乙酰丙酰 (Lev) 基团。新的因素已经被揭示，可以解释 O-6 处 TFB 和五氟苯甲酰基 (PFB) 基团的 α-立体选择性。它们具有构象性质，并通过 DFT 计算得到证实。该供体的潜力以及 TFB 和 Lev 保护基团的正交性通过对应于烟曲霉α-(1 → 3)- d-葡聚糖的α-(1 → 3)-连接五葡萄糖苷的合成得到展示。其六糖衍生物，在非还原端带有β-葡萄糖胺残基。