2-acetamido-2-deoxy-1,4,6-tri-O-pivaloyl-β-D-galactopyranose | 1258839-42-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-acetamido-2-deoxy-1,4,6-tri-O-pivaloyl-β-D-galactopyranose
• 英文别名: pivaloyl(-4)[pivaloyl(-6)]GalNAc(b)-O-pivaloyl；[(2R,3R,4R,5R,6S)-5-acetamido-3,6-bis(2,2-dimethylpropanoyloxy)-4-hydroxyoxan-2-yl]methyl 2,2-dimethylpropanoate
• CAS: 1258839-42-7
• 化学式: C₂₃H₃₉NO₉
• 分子量: 473.564
• InChiKey: MZTSFFRXZUCUDE-MTSZKFMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  138
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2-acetamido-2-deoxy-1,4,6-tri-O-pivaloyl-β-D-galactopyranose 在 吡啶 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 反应 6.5h， 生成 phenyl O-(2-acetamido-3-O-acetyl-2-deoxy-4,6-di-O-pivaloyl-β-D-galactopyranosyl)-(1→3)-2,4,6-tri-O-benzyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  A Protocol for Metal Triflate Catalyzed Direct Glycosylations with GalNAc 1-OPiv Donors

  摘要：

  Herein we report on the development of novel glycosylation methodology for the concise synthesis of naturally occurring glycoconjugate motifs containing N-acetylgalactosamine (GalNAc) from the cheaper and commercially available N-acetylglucosamine (GlcNAc). The stereoselective glycosylations proceed with catalytic amounts of a promoter and without the need for N-protection other than the biologically relevant N-acetyl group. Among the catalysts explored, both Bi(OTf)3 and Fe(OTf)3 were found to be highly active Lewis acids for this reaction. It was also found that other less reactive metal triflates such as those of Cu(II) and Yb(III) can be beneficial in glycosylation reactions on more demanding glycosyl acceptors. We have furthermore demonstrated that it is possible to control the anomeric stereoselectivity in the glycosylation via postglycosylation in situ anomerization to obtain good yields of α-galactosides. The present protocol was used to prepare important naturally occurring carbohydrate motifs, including a trisaccharide fragment of the naturally occurring marine sponge clarhamnoside.

  DOI：

  10.1021/jo502036f
• 作为产物：
  描述：

  2-acetamido-2-deoxy-1,3,6-di-O-pivaloyl-β-D-glucopyranoside 在 吡啶 、 三氟甲磺酸酐 作用下， 以 二氯甲烷 为溶剂， 以3.058 g的产率得到2-acetamido-2-deoxy-1,4,6-tri-O-pivaloyl-β-D-galactopyranose
  参考文献：
  名称：

  d-氨基葡萄糖和d-半乳糖胺β-构型硫代糖苷的形成及受保护的母乳低聚糖的合成

  摘要：

  我们报道了使用催化和无溶剂方法从d - N-乙酰葡糖胺立体选择性多克规模制备 2-叠氮基-2-脱氧-β-d-葡萄糖-和吡喃半乳糖苷的环己基-和苯基硫代糖苷。两种制备的结构单元被用作合成受保护形式的人乳低聚糖 LNT 和 LNnT 的关键中间体。

  DOI：

  10.1021/acs.joc.3c01267

文献信息

• An efficient conversion of N-acetyl-d-glucosamine to N-acetyl-d-galactosamine and derivatives
  作者：Jianhao Feng、Chang-Chun Ling

  DOI：10.1016/j.carres.2010.09.008

  日期：2010.11

  2-Acetamido-2-deoxy-D-galactose (D-GalNAc) is an important monosaccharide widely distributed in nature. However, unlike its 4-epimer, the 2-acetamido-2-deoxy-D-glucose (D-GlcNAc), D-GalNAc is very expensive to obtain from commercial sources. Herein we report an efficient transformation that allows for the conversion of D-GlcNAc to a D-GalNAc derivative 7 in three steps and in 58.4-75% overall yields. The process was carried out on a greater than 20-g scale without the need of chromatography. The versatility of compound 7 was demonstrated by the synthesis of several useful monosaccharides and thiodisaccharides containing a D-GalNAc residue. (C) 2010 Elsevier Ltd. All rights reserved.
• A Protocol for Metal Triflate Catalyzed Direct Glycosylations with GalNAc 1-OPiv Donors
  作者：Michelle R. Rasmussen、Mikkel H. S. Marqvorsen、Steffan K. Kristensen、Henrik H. Jensen

  DOI：10.1021/jo502036f

  日期：2014.11.21

  Herein we report on the development of novel glycosylation methodology for the concise synthesis of naturally occurring glycoconjugate motifs containing N-acetylgalactosamine (GalNAc) from the cheaper and commercially available N-acetylglucosamine (GlcNAc). The stereoselective glycosylations proceed with catalytic amounts of a promoter and without the need for N-protection other than the biologically relevant N-acetyl group. Among the catalysts explored, both Bi(OTf)3 and Fe(OTf)3 were found to be highly active Lewis acids for this reaction. It was also found that other less reactive metal triflates such as those of Cu(II) and Yb(III) can be beneficial in glycosylation reactions on more demanding glycosyl acceptors. We have furthermore demonstrated that it is possible to control the anomeric stereoselectivity in the glycosylation via postglycosylation in situ anomerization to obtain good yields of α-galactosides. The present protocol was used to prepare important naturally occurring carbohydrate motifs, including a trisaccharide fragment of the naturally occurring marine sponge clarhamnoside.
• Formation of β-Configured Thioglycosides of<scp>d</scp>-Glucosamine and<scp>d</scp>-Galactosamine and Synthesis of Protected Human Milk Oligosaccharides
  作者：Kamilla Pedersen、Louise G. Christensen、Henrik H. Jensen

  DOI：10.1021/acs.joc.3c01267

  日期：2023.9.1

  on the stereoselective multigram scale preparation of cyclohexyl- and phenyl thioglycosides of 2-azido-2-deoxy-β-d-gluco- and galactopyranosides from d-N-acetylglucosamine using a catalytic and solvent-free method. Two of the prepared building blocks were used as key intermediates for the synthesis of human milk oligosaccharides LNT and LNnT in their protected form.

  我们报道了使用催化和无溶剂方法从d - N-乙酰葡糖胺立体选择性多克规模制备 2-叠氮基-2-脱氧-β-d-葡萄糖-和吡喃半乳糖苷的环己基-和苯基硫代糖苷。两种制备的结构单元被用作合成受保护形式的人乳低聚糖 LNT 和 LNnT 的关键中间体。