3,4,6-tri-O-benzyl-α-D-mannopyranosyl 2-pyridyl sulfone | 168985-18-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,4,6-tri-O-benzyl-α-D-mannopyranosyl 2-pyridyl sulfone
• CAS: 168985-18-0
• 化学式: C₃₂H₃₃NO₇S
• 分子量: 575.683
• InChiKey: MPGLYXVTAKISNQ-AQTFCTACSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.33
• 重原子数：
  41.0
• 可旋转键数：
  12.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  104.18
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-α-D-mannopyranosyl 2-pyridyl sulfone 在 4-二甲氨基吡啶 、 samarium diiodide 、 四丁基氟化铵 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 (Z)-2-Phenyl-1-(3,4,6-tri-O-benzyl-β-D-mannopyranosyl)ethylene
  参考文献：
  名称：

  1,2-cis-C-glycoside synthesis by samarium diiodide-promoted radical cyclizations

  摘要：

  AbstractThe samarium diiodide reduction of glycosyl pyridyl sulfones bearing a silicon‐tethered unsaturated group at the C2–OH position leads to the stereo‐specific synthesis of 1,2‐cis‐C‐glycosides in good yield after desilylation. These reactions proceed via an anomeric radical with subsequent 5‐exo cyclization. Unlike the corresponding glycosyl phenyl sulfones, the pyridyl derivatives react instantaneously with samarium diiodide and do not require a cosolvent such as hexamethylphosphoramide (HMPA). Under these reaction conditions radical cyclization precedes the second reduction step. Examples of 5‐exo‐trig and ‐dig ring closures are given. The synthetic utility of this method was demonstrated by a short synthesis of methyl C‐isomaltoside.

  DOI：

  10.1002/chem.19970030822
• 作为产物：
  描述：

  3,4,6-三-O-苄基-beta-D-吡喃甘露糖-1,2-(甲基原乙酸酯) 在 碳酸氢钠 、 potassium carbonate 、 间氯过氧苯甲酸 、 mercury dibromide 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 7.0h， 生成 3,4,6-tri-O-benzyl-α-D-mannopyranosyl 2-pyridyl sulfone
  参考文献：
  名称：

  1,2-cis-C-glycoside synthesis by samarium diiodide-promoted radical cyclizations

  摘要：

  AbstractThe samarium diiodide reduction of glycosyl pyridyl sulfones bearing a silicon‐tethered unsaturated group at the C2–OH position leads to the stereo‐specific synthesis of 1,2‐cis‐C‐glycosides in good yield after desilylation. These reactions proceed via an anomeric radical with subsequent 5‐exo cyclization. Unlike the corresponding glycosyl phenyl sulfones, the pyridyl derivatives react instantaneously with samarium diiodide and do not require a cosolvent such as hexamethylphosphoramide (HMPA). Under these reaction conditions radical cyclization precedes the second reduction step. Examples of 5‐exo‐trig and ‐dig ring closures are given. The synthetic utility of this method was demonstrated by a short synthesis of methyl C‐isomaltoside.

  DOI：

  10.1002/chem.19970030822

文献信息

• Further studies in α-C-mannosylation promoted by samarium diiodide
  作者：Olivier Jarreton、Troels Skrydstrup、Jean-Marie Beau

  DOI：10.1016/s0040-4039(97)00206-2

  日期：1997.3

  Mannosyl pyridylsulfones with varying C2OH protecting groups were reacted with cyclohexanone in the presence of SmI2. With SiMe2tBu and Bn, high yields of an α-C-mannoside were obtained. In the former case no β-elimination was observed. The relative configuration of the major diastereomer obtained upon coupling with aldehydes was determined.

  在SmI 2的存在下，具有不同C2 = OH保护基的甘露糖基吡啶基砜与环己酮反应。使用SiMe 2 t Bu和Bn，可获得高收率的α - C-甘露糖苷。在前一种情况下，未观察到β-消除。确定了与醛偶联后获得的主要非对映异构体的相对构型。
• A General Approach to 1,2-trans-C-Glycosides via Glycosyl Samarium(III) Compounds
  作者：Troels Skrydstrup、Olivier Jarreton、Daniel Mazéas、Dominique Urban、Jean-Marie Beau

  DOI：10.1002/(sici)1521-3765(19980416)4:4<655::aid-chem655>3.3.co;2-w

  日期：1998.4.16
• Mazeas, Daniel; Skrydstrup, Troels; Doumeix, Olivier, Angewandte Chemie, 1994, vol. 106, # 13, p. 1457 - 1459
  作者：Mazeas, Daniel、Skrydstrup, Troels、Doumeix, Olivier、Beau, Jean-Marie

  DOI：——

  日期：——
• The stereospecific synthesis of methyl α-C-mannobioside: a potential inhibitor of M. tuberculosis binding to human macrophages
  作者：Olivier Jarreton、Troels Skrydstrup、Jean-Marie Beau

  DOI：10.1039/cc9960001661

  日期：——

  The synthesis of the C-glycoside analogue of the mycobacteria capping disaccharide, Man alpha 1-2Man, employing a glycosyl organosamarium is described.