3,6-二-O-苯甲酰基-D-半乳糖 97 | 130323-36-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3,6-二-O-苯甲酰基-D-半乳糖 97
• 中文别名: 3,6-二-O-苯甲酰基-D-半乳糖97；3,6-二-O-苯甲酰基-D-半乳醛
• 英文名称: 3,6-di-O-benzoyl-D-galactal
• 英文别名: [(2R,3R,4R)-4-benzoyloxy-3-hydroxy-3,4-dihydro-2H-pyran-2-yl]methyl benzoate
• CAS: 130323-36-3
• 化学式: C₂₀H₁₈O₆
• 分子量: 354.359
• InChiKey: MXJFEWOUOTWSTM-KZNAEPCWSA-N

物化性质

• 熔点：
  122-124 °C(lit.)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  82.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,6-二-O-苯甲酰基-D-半乳糖 97 在 Lindlar's catalyst 氢气 作用下， 反应 15.0h， 以80%的产率得到[(2R,3R,4R)-4-benzoyloxy-3-hydroxyoxan-2-yl]methyl benzoate
  参考文献：
  名称：

  一种温和有效的方法，用于区域选择性的甲硅烷基介导的对碳水化合物上C-4羟基的保护-脱保护

  摘要：

  报道了区域选择性路线，其使得六吡喃糖及其衍生物的游离4-OH基团容易且快速地可用。该协议显示出对中间体（例如1a）的高效率，该中间体在C-6处包含TIPS保护基，在C-4处必含苯甲酰基。用TBAF处理1a可裂解TIPS保护基并引起C-4处苯甲酰基向较不拥挤的C-6位置的分子内迁移。

  DOI：

  10.1016/s0040-4039(01)00611-6
• 作为产物：
  描述：

  D-三乙酰半乳糖烯 在 吡啶 、 甲醇 、 sodium 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 1.25h， 生成 3,6-二-O-苯甲酰基-D-半乳糖 97
  参考文献：
  名称：

  Syntheses of the methyl glycosides of the repeating units of chondroitin 4- and 6-sulfate

  摘要：

  3,4,6-Tri-O-acetyl-D-galactal was transformed into methyl 6-O-acetyl-2-azido-4-O-benzyl-2-deoxy-beta-D-galactopyranoside and its 4-O-acetyl-6-O-benzyl analogue, each of which was glycosylated with activated, O-acetylated derivatives of methyl D-glucopyranosyluronate. The resulting beta-(1----3)-linked disaccharide derivatives were each reductively N-acetylated, hydrogenolysed, O-sulfated, and saponified to afford the disodium salts of methyl 2-acetamido-2-deoxy-3-O-(beta-D-glucopyranosyluronic acid)-4-O-sulfo-beta-D-galactopyranoside and the 6-O-sulfo analogue. D-Galactal was also transformed into activated derivatives of 2-azido-3,6-di-O-benzyl-2-deoxy-D-galactopyranose and their 3,4-di-O-benzyl analogues with various substituents at O-4 and O-6. These glycosyl donors were condensed with 6-O-protected derivatives of methyl 2,3-di-O-benzyl-beta-D-glucopyranoside to give the beta-(1----4)-linked disaccharide derivatives, which were selectively deprotected, then oxidised at C-6 of the gluco unit, reductively N-acetylated, selectively deprotected, O-sulfated at C-4 or C-6 of the galacto unit, and hydrogenolysed to give the disodium salts of methyl 4-O-(2-acetamido-2-deoxy-4-O-sulfo-beta-D-galactopyranosyl)-beta-D- glucopyranosiduronic acid and the 6-O-sulfo analogue.

  DOI：

  10.1016/0008-6215(90)84259-w

文献信息

• Synthesis of γ-aminobutyric acid analogs based on carbohydrate scaffolds
  作者：Ming Zhong、Xiang-Bao Meng、Zhong-Jun Li

  DOI：10.1016/j.carres.2010.03.033

  日期：2010.6

  acid analogs based on sugar scaffolds were prepared in six to nine steps starting from D-glucal and D-galactal. The key step in the synthesis is the Vilsmeier-Haack reaction that affords the corresponding 2-C-formyl glycal on treatment with DMF and POCl(3). Oxidation of the aldehyde and reduction of the 4-azido group provided the corresponding GABA analog. Acylamide and tetrazole analogs were also

  基于糖支架的γ-氨基丁酸类似物是从D-葡萄糖和D-半乳糖开始的六到九个步骤中制备的。合成中的关键步骤是Vilsmeier-Haack反应，该反应在用DMF和POCl（3）处理后提供相应的2-C-甲酰基糖基。醛的氧化和4-叠氮基的还原提供了相应的GABA类似物。还制备了酰胺和四唑类似物作为羧酸的生物等排体。
• Kjoelberg, Ove; Neumann, Klaus, Acta Chemica Scandinavica, 1994, vol. 48, # 1, p. 80 - 83
  作者：Kjoelberg, Ove、Neumann, Klaus

  DOI：——

  日期：——
• JACQUINET, JEAN-CLAUDE, CARBOHYDR. RES., 199,(1990) N, C. 153-181
  作者：JACQUINET, JEAN-CLAUDE

  DOI：——

  日期：——
• Syntheses of the methyl glycosides of the repeating units of chondroitin 4- and 6-sulfate
  作者：Jean-Claude Jacquinet

  DOI：10.1016/0008-6215(90)84259-w

  日期：1990.6

  3,4,6-Tri-O-acetyl-D-galactal was transformed into methyl 6-O-acetyl-2-azido-4-O-benzyl-2-deoxy-beta-D-galactopyranoside and its 4-O-acetyl-6-O-benzyl analogue, each of which was glycosylated with activated, O-acetylated derivatives of methyl D-glucopyranosyluronate. The resulting beta-(1----3)-linked disaccharide derivatives were each reductively N-acetylated, hydrogenolysed, O-sulfated, and saponified to afford the disodium salts of methyl 2-acetamido-2-deoxy-3-O-(beta-D-glucopyranosyluronic acid)-4-O-sulfo-beta-D-galactopyranoside and the 6-O-sulfo analogue. D-Galactal was also transformed into activated derivatives of 2-azido-3,6-di-O-benzyl-2-deoxy-D-galactopyranose and their 3,4-di-O-benzyl analogues with various substituents at O-4 and O-6. These glycosyl donors were condensed with 6-O-protected derivatives of methyl 2,3-di-O-benzyl-beta-D-glucopyranoside to give the beta-(1----4)-linked disaccharide derivatives, which were selectively deprotected, then oxidised at C-6 of the gluco unit, reductively N-acetylated, selectively deprotected, O-sulfated at C-4 or C-6 of the galacto unit, and hydrogenolysed to give the disodium salts of methyl 4-O-(2-acetamido-2-deoxy-4-O-sulfo-beta-D-galactopyranosyl)-beta-D- glucopyranosiduronic acid and the 6-O-sulfo analogue.
• A mild and efficient approach for the regioselective silyl-mediated protection–deprotection of C-4 hydroxyl group on carbohydrates
  作者：Andrea Graziani、Pietro Passacantilli、Giovanni Piancatelli、Simona Tani

  DOI：10.1016/s0040-4039(01)00611-6

  日期：2001.6

  This protocol shows high efficiency on intermediates, such as 1a, which contain a TIPS protective group at C-6 and necessarily a benzoyl group at C-4. Treatment of 1a with TBAF cleaves the TIPS protecting group and gives rise to an intramolecular migration of the benzoyl group at C-4 to the less crowded C-6 position.

  报道了区域选择性路线，其使得六吡喃糖及其衍生物的游离4-OH基团容易且快速地可用。该协议显示出对中间体（例如1a）的高效率，该中间体在C-6处包含TIPS保护基，在C-4处必含苯甲酰基。用TBAF处理1a可裂解TIPS保护基并引起C-4处苯甲酰基向较不拥挤的C-6位置的分子内迁移。