(1S,4a'R,7'R,8'R,8a'R)-2',2'-di-tert-butyl-8'-((triethylsilyl)oxy)-5,7,7'-tris((2-(trimethylsilyl)ethoxy)methoxy)-4a',7',8',8a'-tetrahydro-3H,4'H-spiro[isobenzofuran-1,6'-pyrano[3,2-d][1,3,2]dioxasiline] | 1238374-35-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (1S,4a'R,7'R,8'R,8a'R)-2',2'-di-tert-butyl-8'-((triethylsilyl)oxy)-5,7,7'-tris((2-(trimethylsilyl)ethoxy)methoxy)-4a',7',8',8a'-tetrahydro-3H,4'H-spiro[isobenzofuran-1,6'-pyrano[3,2-d][1,3,2]dioxasiline]
• CAS: 1238374-35-0
• 化学式: C₄₅H₈₈O₁₁Si₅
• 分子量: 945.615
• InChiKey: KDTHEXXOLNKEKD-ZVDUXBRRSA-N

物化性质

• 沸点：
  786.8±60.0 °C(predicted)
• 密度：
  1.04±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.7
• 重原子数：
  61.0
• 可旋转键数：
  23.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  101.53
• 氢给体数：
  0.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  (1S,4a'R,7'R,8'R,8a'R)-2',2'-di-tert-butyl-8'-((triethylsilyl)oxy)-5,7,7'-tris((2-(trimethylsilyl)ethoxy)methoxy)-4a',7',8',8a'-tetrahydro-3H,4'H-spiro[isobenzofuran-1,6'-pyrano[3,2-d][1,3,2]dioxasiline] 在 4-甲基苯磺酸吡啶 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以53%的产率得到(1S,4a'R,7'R,8'R,8a'S)-2',2'-di-tert-butyl-5,7,7'-tris((2-(trimethylsilyl)ethoxy)methoxy)-4a',7',8',8a'-tetrahydro-3H,4'H-spiro[isobenzofuran-1,6'-pyrano[3,2-d][1,3,2]dioxasilin]-8'-ol
  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：

  、 2-(三甲基硅烷基)乙氧甲基氯 在 silver trifluoromethanesulfonate 、 四丁基碘化铵 、 N,N-二异丙基乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 以74%的产率得到(1S,4a'R,7'R,8'R,8a'R)-2',2'-di-tert-butyl-8'-((triethylsilyl)oxy)-5,7,7'-tris((2-(trimethylsilyl)ethoxy)methoxy)-4a',7',8',8a'-tetrahydro-3H,4'H-spiro[isobenzofuran-1,6'-pyrano[3,2-d][1,3,2]dioxasiline]
  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