2,6-di-O-pivaloyl-D-galactono-1,4-lactone | 153474-77-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,6-di-O-pivaloyl-D-galactono-1,4-lactone
• 英文别名: [(2R)-2-[(2S,3S,4R)-4-(2,2-dimethylpropanoyloxy)-3-hydroxy-5-oxooxolan-2-yl]-2-hydroxyethyl] 2,2-dimethylpropanoate
• CAS: 153474-77-2
• 化学式: C₁₆H₂₆O₈
• 分子量: 346.378
• InChiKey: FQPQXJODSQZAEK-VPOLOUISSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  119
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,6-di-O-pivaloyl-D-galactono-1,4-lactone 在 吡啶 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 3.17h， 生成 2,3,5,6-tetra-O-benzoyl-β-D-galactofuranosyl-(1->5)-3-O-acetyl-2,6-di-O-pivaloyl-D-galactono-1,4-lactone
  参考文献：
  名称：

  Syntheses of β-d-Galf-(1→6)-β-d-Galf-(1→5)-d-Galf and β-d-Galf-(1→5)-β-d-Galf-(1→6)-d-Galf, Trisaccharide Units in the Galactan of Mycobacterium tuberculosis

  摘要：

  The galactofuran is a crucial constituent of the cell wall of mycobacteria. An efficient synthesis of the two trisaccharide units of the galactan is described. The strategy relies on the use of substituted D-galactono-1,4-lactones as precursors for the internal and the reducing galactofuranoses. Dec-9-enyl beta-D-Galf-(1-->6)-beta-D-Galf-(1-->5)-beta-D-Galf (2) and dec-9-enyl beta-D-Galf-(1-->5)-beta-D-Galf-(1beta6)-beta-D-Galf (9) so far reported as convenient substrates for the galactofaranosyl transferase, and possibly useful for immunological studies, were obtained by the trichloroacetimidate method of glycosylation.

  DOI：

  10.1021/jo034365o
• 作为产物：
  描述：

  三甲基乙酰氯 、 D-半乳糖酸-1,4-内酯 在 吡啶 作用下， 反应 5.0h， 以79%的产率得到2,6-di-O-pivaloyl-D-galactono-1,4-lactone
  参考文献：
  名称：

  Syntheses of β-d-Galf-(1→6)-β-d-Galf-(1→5)-d-Galf and β-d-Galf-(1→5)-β-d-Galf-(1→6)-d-Galf, Trisaccharide Units in the Galactan of Mycobacterium tuberculosis

  摘要：

  The galactofuran is a crucial constituent of the cell wall of mycobacteria. An efficient synthesis of the two trisaccharide units of the galactan is described. The strategy relies on the use of substituted D-galactono-1,4-lactones as precursors for the internal and the reducing galactofuranoses. Dec-9-enyl beta-D-Galf-(1-->6)-beta-D-Galf-(1-->5)-beta-D-Galf (2) and dec-9-enyl beta-D-Galf-(1-->5)-beta-D-Galf-(1beta6)-beta-D-Galf (9) so far reported as convenient substrates for the galactofaranosyl transferase, and possibly useful for immunological studies, were obtained by the trichloroacetimidate method of glycosylation.

  DOI：

  10.1021/jo034365o

文献信息

• Synthesis of arabinofuranose branched galactofuran tetrasaccharides, constituents of mycobacterial arabinogalactan
  作者：Lucía Gandolfi-Donadío、Malena Santos、Rosa M. de Lederkremer、Carola Gallo-Rodriguez

  DOI：10.1039/c0ob00989j

  日期：——

  Mycolyl-arabinogalactan (mAG) complex is a major component of the cell wall of Mycobacterium tuberculosis, the causative agent of tuberculosis disease. Due to the essentiality of the cell wall for mycobacterium viability, knowledge of the biosynthesis of the arabinogalactan is crucial for the development of new therapeutic agents. In this context, we have synthesized two new branched arabinogalactafuranose tetrasaccharides, decenyl β-D-Galf-(1→5)-β-D-Galf-(1→6)[α-D-Araf(1→5)]-β-D-Galf (1) and decenyl β-D-Galf-(1→6)-[α-D-Araf-(1→5)]-β-D-Galf-(1→5)-β-D-Galf (2), as interesting tools for arabinofuranosyl transferase studies. The aldonolactone strategy for the introduction of the internal D-Galf was employed, allowing the construction of oligosaccharides from the non-reducing to the reducing end. Moreover, a one-pot procedure was developed for the synthesis of trisaccharide lactone 21, precursor of 2, which involved a glycosylation-deprotection-glycosylation sequence, through the use of TMSOTf as catalyst of the trichloroacetimidate method as well as promoter of TBDMS deprotection.

  麦角糖阿拉伯半乳糖（mAG）复合物是结核分枝杆菌（Mycobacterium tuberculosis）细胞壁的重要组成部分，该菌是结核病的致病因子。由于细胞壁对分枝杆菌的生存至关重要，因此了解阿拉伯半乳糖的生物合成对于开发新的治疗药物具有重要意义。在此背景下，我们合成了两种新的分支型阿拉伯半乳糖呋喃糖四糖，分别为十烯基 β-D-Galf-(1→5)-β-D-Galf-(1→6)[α-D-Araf(1→5)]-β-D-Galf (1) 和十烯基 β-D-Galf-(1→6)-[α-D-Araf-(1→5)]-β-D-Galf-(1→5)-β-D-Galf (2)，作为阿拉伯呋喃糖基转移酶研究的有趣工具。采用了醇内酯策略引入内源性 D-Galf，使得可以从非还原端到还原端构建寡糖。此外，还开发了一种一锅法合成三糖内酯 21，它是 2 的前体，该方法涉及到糖苷化-去保护-糖苷化序列，采用 TMSOTf 作为三氯乙酰胺法的催化剂，以及 TBDMS 去保护的促进剂。
• Facile synthesis of α-<scp>D</scp>-Ara<i>f-</i>(1→5)-<scp>D</scp>-Gal<i>f</i>, the linker unit of the arabinan to the galactan in <i>Mycobacterium tuberculosis</i>
  作者：Lucía Gandolfi-Donadío、Carola Gallo-Rodriguez、Rosa M de Lederkremer

  DOI：10.1139/v06-025

  日期：2006.4.1

  The arabinogalactan is a crucial constituent of the cell wall of mycobacteria. Both monosaccharides (arabinose and galactose) are found in the furanose configuration, absent in mammals. An efficient synthesis of α-D-Araf-(1→5)-D-Galf, the linker unit of the arabinan to the galactan, is described. The strategy relies on the use of a conveniently substituted D-galactono-1,4-lactone as a precursor of the reducing furanose ring. The glycosylation step was performed by the tin(IV) chloride promoted method using 1,2,3,5-tetra-O-benzoyl-α,β-D-arabinofuranose. The arabinose donor was obtained in a crystalline state in one step by benzoylation of arabinose in hot pyridine. Selective glycosylation of the exocyclic OH-5 was obtained in 75% yield to give 2,3,5-tri-O-benzoyl-α-D-arabinofuranosyl-(1→5)-2,6-di-O-pivaloyl-D-galactono-1,4-lactone. Reduction with disiamylborane gave the disaccharide synthon, useful for further glycosylations. Dec-9-enyl α-D-Araf-(1→5)-β-D-Galf, a convenient substrate for arabinofuranosyl transferases studies, was obtained by the trichloroacetimidate method of glycosylation.Key words: arabinofuranose, galactofuranose, Mycobacterium arabinogalactan, trichloroacetimidate, tin(IV) chloride.

  阿拉伯半乳聚糖是分枝杆菌细胞壁的重要成分。这两种单糖（阿拉伯糖和半乳糖）都以呋喃糖构型存在，哺乳动物中没有这种构型。本文介绍了阿拉伯聚糖与半乳糖的连接单元 α-D-Araf-(1→5)-D-Galf 的高效合成方法。该策略依赖于使用方便取代的 D-半乳糖-1,4-内酯作为还原呋喃糖环的前体。糖基化步骤是通过氯化锡（IV）促进法使用 1,2,3,5-四-O-苯甲酰基-α,β-D-阿拉伯呋喃糖进行的。通过在热吡啶中对阿拉伯糖进行苯甲酰化，一步即可获得结晶状态的阿拉伯糖供体。外环 OH-5 的选择性糖基化得到 2,3,5-三-O-苯甲酰基-α-D-阿拉伯呋喃糖基-(1→5)-2,6-二-O-特戊酰基-D-半乳糖-1,4-内酯，收率为 75%。用二甲基硼烷还原可得到二糖合子，有助于进一步的糖基化。通过三氯乙酰亚氨酸糖基化方法获得了α-D-Araf-(1→5)-β-D-Galf Dec-9-烯基，这是一种方便的阿拉伯呋喃糖基转移酶研究底物。
• Synthesis of a tetrasaccharide fragment of mycobacterial arabinogalactan
  作者：Lucía Gandolfi-Donadío、Carola Gallo-Rodriguez、Rosa M. de Lederkremer

  DOI：10.1016/j.carres.2008.01.024

  日期：2008.7

  conveniently derivatized for further elongation. The strategy relied on the use of suitably substituted D-galactono-1,4-lactones as precursors for the galactofuranose units. Reduction of lactone tetrasaccharide 9 with disiamylborane afforded the tetrasaccharide synthon 1. The tetrasaccharide contains the linker unit of the arabinan to the galactan.

  分枝杆菌的阿拉伯半乳聚糖含有呋喃糖环形式的两种单糖，在哺乳动物中不存在。我们在这里报告四糖片段α-D-Araf-（1-> 5）-beta-D-Galf-（1-> 5）-beta-D-Galf-（1-> 6的首次合成）-D-Galf，可方便地衍生化以进一步延长。该策略依赖于使用适当取代的D-半乳糖-1,4-内酯作为半乳糖呋喃糖单元的前体。用二戊基硼烷还原内酯四糖9得到四糖合成子1。四糖含有阿拉伯聚糖与半乳聚糖的连接单元。
• Gallo, Carola; Jeroncic, Lucio O.; Varela, Oscar, Journal of Carbohydrate Chemistry, 1993, vol. 12, # 7, p. 841 - 852
  作者：Gallo, Carola、Jeroncic, Lucio O.、Varela, Oscar、Lederkremer, Rosa M. de

  DOI：——

  日期：——
• Syntheses of β-<scp>d</scp>-Gal<i>f</i>-(1→6)-β-<scp>d</scp>-Gal<i>f</i>-(1→5)-<scp>d</scp>-Gal<i>f</i> and β-<scp>d</scp>-Gal<i>f</i>-(1→5)-β-<scp>d</scp>-Gal<i>f</i>-(1→6)-<scp>d</scp>-Gal<i>f</i>, Trisaccharide Units in the Galactan of <i>Mycobacterium </i><i>t</i><i>uberculosis</i>
  作者：Lucía Gandolfi-Donadío、Carola Gallo-Rodriguez、Rosa M. de Lederkremer

  DOI：10.1021/jo034365o

  日期：2003.9.1

  The galactofuran is a crucial constituent of the cell wall of mycobacteria. An efficient synthesis of the two trisaccharide units of the galactan is described. The strategy relies on the use of substituted D-galactono-1,4-lactones as precursors for the internal and the reducing galactofuranoses. Dec-9-enyl beta-D-Galf-(1-->6)-beta-D-Galf-(1-->5)-beta-D-Galf (2) and dec-9-enyl beta-D-Galf-(1-->5)-beta-D-Galf-(1beta6)-beta-D-Galf (9) so far reported as convenient substrates for the galactofaranosyl transferase, and possibly useful for immunological studies, were obtained by the trichloroacetimidate method of glycosylation.