[(3S,4'aR,7'R,8'R,8'aR)-2',2'-ditert-butyl-4,6,7'-tris(2-trimethylsilylethoxycarbonyloxy)spiro[1H-2-benzofuran-3,6'-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3,2]dioxasiline]-8'-yl] (2E,4E,7S,8E,10E,14S)-8,14-dimethyl-7-triethylsilyloxyhexadeca-2,4,8,10-tetraenoate | 934243-79-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 糖脂
• 英文名称: [(3S,4'aR,7'R,8'R,8'aR)-2',2'-ditert-butyl-4,6,7'-tris(2-trimethylsilylethoxycarbonyloxy)spiro[1H-2-benzofuran-3,6'-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3,2]dioxasiline]-8'-yl] (2E,4E,7S,8E,10E,14S)-8,14-dimethyl-7-triethylsilyloxyhexadeca-2,4,8,10-tetraenoate
• CAS: 934243-79-5
• 化学式: C₆₃H₁₀₈O₁₆Si₅
• 分子量: 1261.97
• InChiKey: UKMRPTPLDUBRCS-SNMPDIQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.93
• 重原子数：
  84
• 可旋转键数：
  37
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  179
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  [(3S,4'aR,7'R,8'R,8'aR)-2',2'-ditert-butyl-4,6,7'-tris(2-trimethylsilylethoxycarbonyloxy)spiro[1H-2-benzofuran-3,6'-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3,2]dioxasiline]-8'-yl] (2E,4E,7S,8E,10E,14S)-8,14-dimethyl-7-triethylsilyloxyhexadeca-2,4,8,10-tetraenoate 在 triethylamine tris(hydrogen fluoride) 作用下， 以 二甲基亚砜 为溶剂， 反应 18.08h， 以89%的产率得到(+)-papulacandin D
  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：

  (5S,12S)-(2E,6E,8E)-5-hydroxy-6,12-dimethyltetradecatrienal 在 lutidine 、 2,4,6-三氯苯甲酰氯 、 potassium trimethylsilonate 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 33.0h， 生成 [(3S,4'aR,7'R,8'R,8'aR)-2',2'-ditert-butyl-4,6,7'-tris(2-trimethylsilylethoxycarbonyloxy)spiro[1H-2-benzofuran-3,6'-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3,2]dioxasiline]-8'-yl] (2E,4E,7S,8E,10E,14S)-8,14-dimethyl-7-triethylsilyloxyhexadeca-2,4,8,10-tetraenoate
  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、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.
• 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.