tetramethyl (2,3-O-isopropylidene-L-tartaroyl)bis(methylphosphonate) | 162052-26-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: tetramethyl (2,3-O-isopropylidene-L-tartaroyl)bis(methylphosphonate)
• 英文别名: 2-dimethoxyphosphoryl-1-[(4R,5R)-5-(2-dimethoxyphosphorylacetyl)-2,2-dimethyl-1,3-dioxolan-4-yl]ethanone
• CAS: 162052-26-8
• 化学式: C₁₃H₂₄O₁₀P₂
• 分子量: 402.275
• InChiKey: MURVTXYVIFOMCU-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.5
• 重原子数：
  25
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  tetramethyl (2,3-O-isopropylidene-L-tartaroyl)bis(methylphosphonate) 、 2,3-二氟-6-硝基苯胺 在 caesium carbonate 作用下， 以 异丙醇 为溶剂， 反应 8.0h， 以54%的产率得到(E)-3-[(4R,5S)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]-1-[(4R,5R)-5-[(E)-3-[(4R,5S)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enoyl]-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-en-1-one
  参考文献：
  名称：

  Preparation of Sugar-Derived .beta.-Keto Phosphonates and Their Use in the Synthesis of Higher Sugars

  摘要：

  Sugar-derived beta-keto phosphonates 5, 6, 7, and 8 were synthesised by the acylation of lithium dimethyl methylphosphonate with the corresponding methyl glycuronates 1, 2, and 3 and glyconate 4 in THF at -78 degrees C, respectively. Wadsworth-Emmons reaction of 5, 6, 7, and 8 with various sugar-derived aldehydes proceeded in good yield to produce higher sugar enones. Similarly, C-2 symmetric bis phosphonate 28 derived from L-tartrate 27 was prepared and condensed with various sugar-derived aldehydes to provide C-2 symmetric bis enones in moderate yields. Treatment of the glucose-derived beta-keto phosphonate 5 with various aldehydes and excess Cs2CO3 resulted in complete cis elimination of the C-4 benzyl group along with the Wadsworth-Emmons reaction, leading to cross-conjugated dienones.

  DOI：

  10.1021/jo00100a047
• 作为产物：
  描述：

  (4R,5R)-4,5-二乙氧基羰基-2,2-二甲基二氧 、 甲基膦酸二甲酯 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 tetramethyl (2,3-O-isopropylidene-L-tartaroyl)bis(methylphosphonate)
  参考文献：
  名称：

  Preparation of Sugar-Derived .beta.-Keto Phosphonates and Their Use in the Synthesis of Higher Sugars

  摘要：

  Sugar-derived beta-keto phosphonates 5, 6, 7, and 8 were synthesised by the acylation of lithium dimethyl methylphosphonate with the corresponding methyl glycuronates 1, 2, and 3 and glyconate 4 in THF at -78 degrees C, respectively. Wadsworth-Emmons reaction of 5, 6, 7, and 8 with various sugar-derived aldehydes proceeded in good yield to produce higher sugar enones. Similarly, C-2 symmetric bis phosphonate 28 derived from L-tartrate 27 was prepared and condensed with various sugar-derived aldehydes to provide C-2 symmetric bis enones in moderate yields. Treatment of the glucose-derived beta-keto phosphonate 5 with various aldehydes and excess Cs2CO3 resulted in complete cis elimination of the C-4 benzyl group along with the Wadsworth-Emmons reaction, leading to cross-conjugated dienones.

  DOI：

  10.1021/jo00100a047

文献信息

• Preparation of Sugar-Derived .beta.-Keto Phosphonates and Their Use in the Synthesis of Higher Sugars
  作者：K. Narkunan、M. Nagarajan

  DOI：10.1021/jo00100a047

  日期：1994.10

  Sugar-derived beta-keto phosphonates 5, 6, 7, and 8 were synthesised by the acylation of lithium dimethyl methylphosphonate with the corresponding methyl glycuronates 1, 2, and 3 and glyconate 4 in THF at -78 degrees C, respectively. Wadsworth-Emmons reaction of 5, 6, 7, and 8 with various sugar-derived aldehydes proceeded in good yield to produce higher sugar enones. Similarly, C-2 symmetric bis phosphonate 28 derived from L-tartrate 27 was prepared and condensed with various sugar-derived aldehydes to provide C-2 symmetric bis enones in moderate yields. Treatment of the glucose-derived beta-keto phosphonate 5 with various aldehydes and excess Cs2CO3 resulted in complete cis elimination of the C-4 benzyl group along with the Wadsworth-Emmons reaction, leading to cross-conjugated dienones.