1,5-anhydro-1-dimethyl(hydroxyl)silyl-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-D-arabino-hex-1-enitol | 1238373-50-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: 1,5-anhydro-1-dimethyl(hydroxyl)silyl-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-D-arabino-hex-1-enitol
• CAS: 1238373-50-6
• 化学式: C₂₀H₄₀O₅Si₂
• 分子量: 416.706
• InChiKey: MGUWGIQRWGHMMQ-LMMKCTJWSA-N

物化性质

• 沸点：
  449.0±45.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.72
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2-iodo-3,5-dimethoxy-1-(tetrahydropyran-2-yl)oxymethylbenzene 、 1,5-anhydro-1-dimethyl(hydroxyl)silyl-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-D-arabino-hex-1-enitol 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以70%的产率得到1,5-anhydro-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-1-(4,6-dimethoxy-2-(tetrahydropyran-2-yl)oxymethyl)-D-arabino-hex-1-enitol
  参考文献：
  名称：

  Total synthesis of (+)-papulacandin D

  摘要：

  A total synthesis of (+)-papulacandin D has been achieved in 31 steps, in a 9.2% overall yield from commercially available materials. The synthetic strategy divided the molecule into two nearly equal sized subunits, the spirocyclic C-arylglycopyranoside and the polyunsaturated fatty acid side-chain. The C-arylglycopyranoside was prepared in 11 steps in a 30% overall yield from triacetoxyglucal. The fatty acid side-chain was also prepared in 11 steps in a 30% overall yield from geraniol. The key strategic transformations in the synthesis are: (1) a palladium-catalyzed, organosilanolate-based cross-coupling reaction of a dimethylglucal-silanol with an electron-rich and sterically hindered aromatic iodide and (2) a Lewis-base catalyzed, enantioselective allylation reaction of a dienal and allyltrichlorosilane. A critical element in the successful execution of the synthesis was the development of a suitable protecting group strategy that satisfied a number of stringent criteria. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.03.093
• 作为产物：
  描述：

  1,5-anhydro-1-dimethylsilyl-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-D-arabino-hex-1-enitol 在 [Ru(p-cymene)Cl₂]₂ 、 水 、 氧气 作用下， 以 乙腈 为溶剂， 反应 0.5h， 以61%的产率得到1,5-anhydro-1-dimethyl(hydroxyl)silyl-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-D-arabino-hex-1-enitol
  参考文献：
  名称：

  Total synthesis of (+)-papulacandin D

  摘要：

  A total synthesis of (+)-papulacandin D has been achieved in 31 steps, in a 9.2% overall yield from commercially available materials. The synthetic strategy divided the molecule into two nearly equal sized subunits, the spirocyclic C-arylglycopyranoside and the polyunsaturated fatty acid side-chain. The C-arylglycopyranoside was prepared in 11 steps in a 30% overall yield from triacetoxyglucal. The fatty acid side-chain was also prepared in 11 steps in a 30% overall yield from geraniol. The key strategic transformations in the synthesis are: (1) a palladium-catalyzed, organosilanolate-based cross-coupling reaction of a dimethylglucal-silanol with an electron-rich and sterically hindered aromatic iodide and (2) a Lewis-base catalyzed, enantioselective allylation reaction of a dienal and allyltrichlorosilane. A critical element in the successful execution of the synthesis was the development of a suitable protecting group strategy that satisfied a number of stringent criteria. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.03.093