Benzyl 6-O-pivaloyl-β-D-galactopyranoside | 139525-91-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Benzyl 6-O-pivaloyl-β-D-galactopyranoside
• 英文别名: [(2R,3R,4S,5R,6R)-3,4,5-trihydroxy-6-phenylmethoxyoxan-2-yl]methyl 2,2-dimethylpropanoate
• CAS: 139525-91-0
• 化学式: C₁₈H₂₆O₇
• 分子量: 354.4
• InChiKey: DVFOEYZKYYXLGH-LYYZXLFJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  105
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Benzyl 6-O-pivaloyl-β-D-galactopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 、 3 A molecular sieve 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 20.0h， 生成 Benzyl [methyl (N-acetyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-α-ulopyranosyl)onate]-(2->3)-6-O-pivaloyl-2,4-di-O-acetyl-β-D-galactopyranoside
  参考文献：
  名称：

  The 2-Naphthylmethyl (NAP) Group in Carbohydrate Synthesis: First Total Synthesis of the GlyCAM-1 Oligosaccharide Structures

  摘要：

  Total syntheses of the GlyCAM-1 (glycosylation-dependent cell adhesion molecule-1) oligosaccharide structures: [alpha-NeuAc-(2 --> 3)-beta-Gal-(1 --> 4)-[alpha-Fuc-(1 --> 3)]-beta-(6-O-SO3Na)-GlcNAc-(1 --> 6)]-[alpha-NeuAc-(2 --> 3)-beta-Gal-(1 --> 3)]-alpha-GalNAc-OMe (1) and [alpha-NeuAc-(2 --> 3)-beta-Gal-(1 --> 4)-[alpha-Fuc-(1 --> 3)]-beta-GlcNAc-(1 --> 6)]-[alpha-NeuAc-(2 3)-beta-Gal-(1 --> 3)]-alpha-GalNAc-OMe (2) through a novel sialyl LewisX tetrasaccharide donor are described. Employing sequential glycosylation strategy, the starting trisaccharide was regio- and stereoselectively constructed through coupling of a disaccharide imidate with the monosaccharide acceptor phenyl-6-O-naphthylmethyl-2-deoxy-2-phthalimido-1-thio-beta-D-glucopyranoside with TMSOTf as a catalyst without affecting the SPh group. The novel sialyl Lewisx tetrasaccharide donor 3 was then obtained by alpha-L-fucosylation of trisaccharide acceptor with the 2,3,4-tri-O-benzyl-1-thio-beta-L-fucoside donor. The structure of the novel sialyl Lewisx tetrasaccharide was established by a combination of 2D DQF-COSY and 2D ROESY experiments. Target oligosaccharides 1 and 2 were eventually constructed through heptasaccharide which was obtained by regioselective assembly of advanced sialyl Lewisx tetrasaccharide donor 3 and a sialylated trisaccharide acceptor in a predictable and controlled manner. Finally, target heptasaccharides 1 and 2 were fully characterized by 2D DQF-COSY, 2D ROESY, HSQC, HMBC experiments and FAB mass spectroscopy.

  DOI：

  10.1002/1521-3765(20010119)7:2<356::aid-chem356>3.0.co;2-e
• 作为产物：
  描述：

  苄基Beta-D-吡喃半乳糖苷 在 吡啶 、 D(+)-10-樟脑磺酸 、 溶剂黄146 作用下， 反应 61.5h， 生成 Benzyl 6-O-pivaloyl-β-D-galactopyranoside
  参考文献：
  名称：

  The 2-Naphthylmethyl (NAP) Group in Carbohydrate Synthesis: First Total Synthesis of the GlyCAM-1 Oligosaccharide Structures

  摘要：

  Total syntheses of the GlyCAM-1 (glycosylation-dependent cell adhesion molecule-1) oligosaccharide structures: [alpha-NeuAc-(2 --> 3)-beta-Gal-(1 --> 4)-[alpha-Fuc-(1 --> 3)]-beta-(6-O-SO3Na)-GlcNAc-(1 --> 6)]-[alpha-NeuAc-(2 --> 3)-beta-Gal-(1 --> 3)]-alpha-GalNAc-OMe (1) and [alpha-NeuAc-(2 --> 3)-beta-Gal-(1 --> 4)-[alpha-Fuc-(1 --> 3)]-beta-GlcNAc-(1 --> 6)]-[alpha-NeuAc-(2 3)-beta-Gal-(1 --> 3)]-alpha-GalNAc-OMe (2) through a novel sialyl LewisX tetrasaccharide donor are described. Employing sequential glycosylation strategy, the starting trisaccharide was regio- and stereoselectively constructed through coupling of a disaccharide imidate with the monosaccharide acceptor phenyl-6-O-naphthylmethyl-2-deoxy-2-phthalimido-1-thio-beta-D-glucopyranoside with TMSOTf as a catalyst without affecting the SPh group. The novel sialyl Lewisx tetrasaccharide donor 3 was then obtained by alpha-L-fucosylation of trisaccharide acceptor with the 2,3,4-tri-O-benzyl-1-thio-beta-L-fucoside donor. The structure of the novel sialyl Lewisx tetrasaccharide was established by a combination of 2D DQF-COSY and 2D ROESY experiments. Target oligosaccharides 1 and 2 were eventually constructed through heptasaccharide which was obtained by regioselective assembly of advanced sialyl Lewisx tetrasaccharide donor 3 and a sialylated trisaccharide acceptor in a predictable and controlled manner. Finally, target heptasaccharides 1 and 2 were fully characterized by 2D DQF-COSY, 2D ROESY, HSQC, HMBC experiments and FAB mass spectroscopy.

  DOI：

  10.1002/1521-3765(20010119)7:2<356::aid-chem356>3.0.co;2-e

文献信息

• Acyl Group Migration and Cleavage in Selectively Protected β-<scp>d</scp>-Galactopyranosides as Studied by NMR Spectroscopy and Kinetic Calculations
  作者：Mattias U. Roslund、Olli Aitio、Johan Wärnå、Hannu Maaheimo、Dmitry Yu. Murzin、Reko Leino

  DOI：10.1021/ja801177s

  日期：2008.7.1

  protective groups and their relative stabilities at variable pH for a series of beta- d-galactopyranoses were studied by NMR spectroscopy. The clockwise and counterclockwise migration rates for the different ester groups were accurately determined by use of a kinetic model. The results presented provide new insights into the acid and base stabilities of commonly used ester protecting groups and the phenomenon

  通过NMR光谱研究了一系列β-d-吡喃半乳糖的乙酰基、新戊酰基和苯甲酰基保护基团的迁移及其在可变pH下的相对稳定性。不同酯基的顺时针和逆时针迁移速率通过使用动力学模型准确确定。所呈现的结果为常用酯保护基团的酸碱稳定性和酰基迁移现象提供了新的见解，并可能有助于规划合成策略。
• Studies Directed toward the Synthesis of Polysialogangliosides: The Regio- and Stereocontrolled Synthesis of Rationally Designed Fragments of the Tetrasialoganglioside GQ_1b⁺.
  作者：Yukishige Ito、Shigeki Nunomura、Shohei Shibayama、Tomoya Ogawa

  DOI：10.1021/jo00032a601

  日期：1992.3

  The synthesis of suitably protected fragments of the tetrasialoganglioside GQ1b (I), i.e., 1 (alpha-NeuAc2 -->-8-alpha-NeuAc2 --> 3-beta-Gal1 --> 4Glc), 2 (alpha-NeuAc2 --> 8-alpha-NeuAc2 --> 3Gal), 3 (GalNAc), 4 (alpha-NeuAc2 --> 8NeuAc), 5 (beta-Gal1 -->- 3GalNAc), and 42 [beta-Gal1 --> 3-beta-GalNAc1 --> 4(alpha-NeuAc2 --> 3)beta-Gal --> 4Glc], is described. All are rationally designed so that the protecting groups can be regioselectively introduced and removed, as needed, before or after the stereoselective coupling of an appropriate pair of fragments. The syntheses of 1, 2, and 4 all feature stereoselective glycosylations by glycosyl donors that bear a C-3 thiophenoxy stereocontrolling auxiliary. Compound 3 was prepared from the D-glucosamine derivative 17 by way of a novel intramolecular nucleophilic displacement with inversion of configuration. Furthermore, model glycosylations of 4-hydroxygalactose derivatives, in which the thioglycoside 3 and the fluoride 40 served as glycosyl donors, were performed. The reaction of 3 with the glycosyl acceptor 30 gave the disaccharide 31 (GalNAc-beta-1 --> 4Gal), whereas that of 40 with 41 afforded the pentasaccharide 42.
• The 2-Naphthylmethyl (NAP) Group in Carbohydrate Synthesis: First Total Synthesis of the GlyCAM-1 Oligosaccharide Structures
  作者：Jie Xia、James L. Alderfer、Conrad. F. Piskorz、Khushi L. Matta

  DOI：10.1002/1521-3765(20010119)7:2<356::aid-chem356>3.0.co;2-e

  日期：2001.1.19

  Total syntheses of the GlyCAM-1 (glycosylation-dependent cell adhesion molecule-1) oligosaccharide structures: [alpha-NeuAc-(2 --> 3)-beta-Gal-(1 --> 4)-[alpha-Fuc-(1 --> 3)]-beta-(6-O-SO3Na)-GlcNAc-(1 --> 6)]-[alpha-NeuAc-(2 --> 3)-beta-Gal-(1 --> 3)]-alpha-GalNAc-OMe (1) and [alpha-NeuAc-(2 --> 3)-beta-Gal-(1 --> 4)-[alpha-Fuc-(1 --> 3)]-beta-GlcNAc-(1 --> 6)]-[alpha-NeuAc-(2 3)-beta-Gal-(1 --> 3)]-alpha-GalNAc-OMe (2) through a novel sialyl LewisX tetrasaccharide donor are described. Employing sequential glycosylation strategy, the starting trisaccharide was regio- and stereoselectively constructed through coupling of a disaccharide imidate with the monosaccharide acceptor phenyl-6-O-naphthylmethyl-2-deoxy-2-phthalimido-1-thio-beta-D-glucopyranoside with TMSOTf as a catalyst without affecting the SPh group. The novel sialyl Lewisx tetrasaccharide donor 3 was then obtained by alpha-L-fucosylation of trisaccharide acceptor with the 2,3,4-tri-O-benzyl-1-thio-beta-L-fucoside donor. The structure of the novel sialyl Lewisx tetrasaccharide was established by a combination of 2D DQF-COSY and 2D ROESY experiments. Target oligosaccharides 1 and 2 were eventually constructed through heptasaccharide which was obtained by regioselective assembly of advanced sialyl Lewisx tetrasaccharide donor 3 and a sialylated trisaccharide acceptor in a predictable and controlled manner. Finally, target heptasaccharides 1 and 2 were fully characterized by 2D DQF-COSY, 2D ROESY, HSQC, HMBC experiments and FAB mass spectroscopy.