(2R,3R,4R,5R,6R)-3-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-carbaldehyde | 160701-91-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,4R,5R,6R)-3-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-carbaldehyde
• 英文别名: (2R,3R,4R,5R,6R)-3-azido-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxane-2-carbaldehyde
• CAS: 160701-91-7
• 化学式: C₂₈H₂₉N₃O₅
• 分子量: 487.555
• InChiKey: VCCQOEFLYRPVOZ-IEAFHPEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  68.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2R,3R,4R,5R,6R)-3-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-carbaldehyde 在 N-溴代丁二酰亚胺(NBS) 、 HN₃O*ClH 、 sodium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 3,4-Bis-((2R,3S,4R,5R,6R)-3-azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-yl)-furazan 2-oxide
  参考文献：
  名称：

  作为糖基腈氧化物和硝酮前体的甲酰基 C-糖苷

  摘要：

  通过糖内酯的噻唑基甲酰化三步制备甲酰基 C-糖苷，很容易与 N-苄基羟胺和羟胺缩合，分别得到相应的糖基硝酮和肟。后一种亚氨基衍生物是通过 N-溴代琥珀酰亚胺法生成腈氧化物的前体。

  DOI：

  10.1055/s-2002-33643
• 作为产物：
  描述：

  2-((2R,3R,4R,5R,6R)-3-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-yl)-3-methyl-thiazolidine 在 水 、 mercury dichloride 作用下， 以 乙腈 为溶剂， 反应 0.25h， 生成 (2R,3R,4R,5R,6R)-3-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-carbaldehyde
  参考文献：
  名称：

  Thiazole-Based Synthesis of Formyl C-Glycosides

  摘要：

  A method for the installation of the formyl group at the anomeric position of pyranoses and furanoses starting from the corresponding lactones has been developed. The strategy involves the addition of 2-lithiothiazole to the sugar lactone, followed by the silane reduction of the acetylated resultant ketol and the unmasking of the formyl group from the thiazole ring. All steps have been studied in some details to improve chemical efficiency and stereochemical control. Hence, reversed alpha:beta ratios of ketols were found in kinetic and thermodynamic mixtures, the former being consistent with a steric effect control of the substituents and the latter by the electronic effect of the ring oxygen. Seven sugar aldehydes with different D-pyranosidic (2,3,4,6-tetra-O-benzyl-gluco, -galacto, and -manno, 2-azido-3,4,6-tri-O-benzyl-2-deoxy-galacto) and D-furanosidic moieties (5-O-benzyl-2,3-isopropylidene-ribo; 2,3,5-tri-O-benzyl-ribo; 2,3:5,6-di-O-isopropylidene-manno) were prepared in 52-65% isolated overall yield from the corresponding lactone.

  DOI：

  10.1021/jo00100a050

文献信息

• Synthesis of α- and β-<scp>d</scp>-(1→6)-<i>C</i>-Disaccharides by Wittig Olefination of Formyl <i>C</i>-Glycosides with Glycopyranose 6-Phosphoranes
  作者：Alessandro Dondoni、Helene M. Zuurmond、Alessia Boscarato

  DOI：10.1021/jo971177n

  日期：1997.11.1

  The synthesis of (1-->6)-C-disaccharides by Wittig condensation of formyl C-glycofuranosides and pyranosides with galacto-and glucopyranose B-phosphoranes is described herein. The method involves the coupling of the sugar aldehydes with the ylides and the reduction of the double bond of the resulting sugar alkenes, in most of the cases by catalytic hydrogenation. The reduction with nickel boride or diimide is employed in some special cases. O-Benzyl protective groups are removed by catalytic hydrogenation either in the course of the reduction of the double bond or in a subsequent step, while O-isopropylidene groups are cleaved by treatment with Amberlite IR-120. In this way, eight free beta-D-(1-->6)-C-disaccharides have been prepared in 26-61% overall yield starting from B-linked formyl C-glycosides. These include C-linked analogues of the biologically active disaccharides allolactose (Gal beta 1,6Glc), gentiobiose (Glc beta 1,6Glc), and N-acetylamino disaccharides (GalNHAc beta,6Gal and GalNHAc beta 1,6Glc). Moreover, the synthesis of two alpha-D-(1-->6)-C-disaccharides is described from formyl C-furanosides. The limiting condition of the synthesis of these stereoisomers is the configurational instability of the alpha-linked formyl C-glycosides under the basic conditions of the Wittig olefination.
• Thiazole-Based Synthesis of Formyl C-Glycosides
  作者：Alessandro Dondoni、Marie-Christine Scherrmann

  DOI：10.1021/jo00100a050

  日期：1994.10

  A method for the installation of the formyl group at the anomeric position of pyranoses and furanoses starting from the corresponding lactones has been developed. The strategy involves the addition of 2-lithiothiazole to the sugar lactone, followed by the silane reduction of the acetylated resultant ketol and the unmasking of the formyl group from the thiazole ring. All steps have been studied in some details to improve chemical efficiency and stereochemical control. Hence, reversed alpha:beta ratios of ketols were found in kinetic and thermodynamic mixtures, the former being consistent with a steric effect control of the substituents and the latter by the electronic effect of the ring oxygen. Seven sugar aldehydes with different D-pyranosidic (2,3,4,6-tetra-O-benzyl-gluco, -galacto, and -manno, 2-azido-3,4,6-tri-O-benzyl-2-deoxy-galacto) and D-furanosidic moieties (5-O-benzyl-2,3-isopropylidene-ribo; 2,3,5-tri-O-benzyl-ribo; 2,3:5,6-di-O-isopropylidene-manno) were prepared in 52-65% isolated overall yield from the corresponding lactone.
• Formyl<i>C</i>-Glycosides as Precursors to Glycosyl Nitrile Oxides and Nitrones
  作者：Alessandro Dondoni、Pier Paolo Giovannini

  DOI：10.1055/s-2002-33643

  日期：——

  three steps, are readily condensed with N-benzylhydroxylamine and hydroxylamine to give the corresponding glycosyl nitrones and oximes respectively. The latter imino derivatives are the precursors to nitrile oxides via the N-bromosuccinimide method.

  通过糖内酯的噻唑基甲酰化三步制备甲酰基 C-糖苷，很容易与 N-苄基羟胺和羟胺缩合，分别得到相应的糖基硝酮和肟。后一种亚氨基衍生物是通过 N-溴代琥珀酰亚胺法生成腈氧化物的前体。