2',2'-bis(1,1-dimethylethyl)-4'a,7',8',8'a-tetrahydro-5,7-bis(2-trimethylsilylethoxycarbonyloxy)-7'-(2-trimethylsilylethoxycarbonyloxy)-8'-hydroxy-(1S,4'aR,7'R,8'R,8'aS)-spiro[isobenzofuran-1(3H),6'(4'H)-pyrano[3,2-d][1,3,2]dioxasiline] | 1053626-65-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异香豆素
• 英文名称: 2',2'-bis(1,1-dimethylethyl)-4'a,7',8',8'a-tetrahydro-5,7-bis(2-trimethylsilylethoxycarbonyloxy)-7'-(2-trimethylsilylethoxycarbonyloxy)-8'-hydroxy-(1S,4'aR,7'R,8'R,8'aS)-spiro[isobenzofuran-1(3H),6'(4'H)-pyrano[3,2-d][1,3,2]dioxasiline]
• 英文别名: [(1S,4'aR,7'R,8'R,8'aS)-2',2'-ditert-butyl-8'-hydroxy-7,7'-bis(2-trimethylsilylethoxycarbonyloxy)spiro[3H-2-benzofuran-1,6'-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3,2]dioxasiline]-5-yl] 2-trimethylsilylethyl carbonate
• CAS: 1053626-65-5
• 化学式: C₃₉H₆₈O₁₄Si₄
• 分子量: 873.303
• InChiKey: YCMZIQWSBDXMTR-FQFYCNANSA-N

物化性质

• 熔点：
  51-54 °C(Solvent: Hexane; Ethyl acetate)
• 沸点：
  821.6±65.0 °C(predicted)
• 密度：
  1.15±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.15
• 重原子数：
  57
• 可旋转键数：
  20
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  164
• 氢给体数：
  1
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  2',2'-bis(1,1-dimethylethyl)-4'a,7',8',8'a-tetrahydro-5,7-bis(2-trimethylsilylethoxycarbonyloxy)-7'-(2-trimethylsilylethoxycarbonyloxy)-8'-hydroxy-(1S,4'aR,7'R,8'R,8'aS)-spiro[isobenzofuran-1(3H),6'(4'H)-pyrano[3,2-d][1,3,2]dioxasiline] 在 2,4,6-三氯苯甲酰氯 、 氢氟酸 、 三乙胺 作用下， 以 二甲基亚砜 、 甲苯 为溶剂， 反应 22.0h， 生成 (+)-papulacandin D
  参考文献：
  名称：

  Total Synthesis of Papulacandin D

  摘要：

  A total synthesis of the antifungal agent papulacandin D is reported. The molecule is representative of a large class of C-aryl glycosides that exhibit significant antifungal activity. The synthetic strategy bifurcates the molecule into two nearly equal subunits, the arylglycoside and 18-carbon fatty acid side chain. The key strategic transformations are (1) the palladium catalyzed, organosilanolate-based cross-coupling of a protected glucal silanol and (2) a catalytic enantioselective allylation of a dienal using allyltrichlorosilane. The synthesis was accomplished in 31 steps overall from commercial starting materials to afford over 50 mg of the natural product.

  DOI：

  10.1021/ja070071z
• 作为产物：
  描述：

  2-(三甲硅基)乙醇 在 palladium on activated charcoal 4-二甲氨基吡啶 、 氢气 、 碳酸氢钠 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 氯仿 为溶剂， -56.0~20.0 ℃ 、101.33 kPa 条件下， 反应 51.0h， 生成 2',2'-bis(1,1-dimethylethyl)-4'a,7',8',8'a-tetrahydro-5,7-bis(2-trimethylsilylethoxycarbonyloxy)-7'-(2-trimethylsilylethoxycarbonyloxy)-8'-hydroxy-(1S,4'aR,7'R,8'R,8'aS)-spiro[isobenzofuran-1(3H),6'(4'H)-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 the antifungal agent papulacandin D is reported. The molecule is representative of a large class of C-aryl glycosides that exhibit significant antifungal activity. The synthetic strategy bifurcates the molecule into two nearly equal subunits, the arylglycoside and 18-carbon fatty acid side chain. The key strategic transformations are (1) the palladium catalyzed, organosilanolate-based cross-coupling of a protected glucal silanol and (2) a catalytic enantioselective allylation of a dienal using allyltrichlorosilane. The synthesis was accomplished in 31 steps overall from commercial starting materials to afford over 50 mg of the natural product.

  DOI：

  10.1021/ja070071z

文献信息

• Total synthesis of (+)-papulacandin D
  作者：Scott E. Denmark、Tetsuya Kobayashi、Christopher S. Regens

  DOI：10.1016/j.tet.2010.03.093

  日期：2010.6

  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.
• Total Synthesis of Papulacandin D
  作者：Scott E. Denmark、Christopher S. Regens、Tetsuya Kobayashi

  DOI：10.1021/ja070071z

  日期：2007.3.1

  A total synthesis of the antifungal agent papulacandin D is reported. The molecule is representative of a large class of C-aryl glycosides that exhibit significant antifungal activity. The synthetic strategy bifurcates the molecule into two nearly equal subunits, the arylglycoside and 18-carbon fatty acid side chain. The key strategic transformations are (1) the palladium catalyzed, organosilanolate-based cross-coupling of a protected glucal silanol and (2) a catalytic enantioselective allylation of a dienal using allyltrichlorosilane. The synthesis was accomplished in 31 steps overall from commercial starting materials to afford over 50 mg of the natural product.