1,5-anhydro-4,6-O-[bis(1,1-dimethylethyl)silylene]-1-C-[2',4'-bis(phenylmethoxy)-6'-(hydroxymethyl)phenyl]-2-deoxy-3-O-triethylsilyl-D-arabino-1-hexenitol | 934243-71-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1,5-anhydro-4,6-O-[bis(1,1-dimethylethyl)silylene]-1-C-[2',4'-bis(phenylmethoxy)-6'-(hydroxymethyl)phenyl]-2-deoxy-3-O-triethylsilyl-D-arabino-1-hexenitol
• 英文别名: [2-[(4aR,8R,8aR)-2,2-ditert-butyl-8-triethylsilyloxy-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3,2]dioxasilin-6-yl]-3,5-bis(phenylmethoxy)phenyl]methanol
• CAS: 934243-71-7
• 化学式: C₄₁H₅₈O₇Si₂
• 分子量: 719.078
• InChiKey: JVSPRVQLBKOXTQ-BMJIQSQISA-N

物化性质

• 熔点：
  50-51 °C(Solvent: Hexane)
• 沸点：
  743.2±60.0 °C(predicted)
• 密度：
  1.12±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.92
• 重原子数：
  50
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  75.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1,5-anhydro-4,6-O-[bis(1,1-dimethylethyl)silylene]-1-C-[2',4'-bis(phenylmethoxy)-6'-(hydroxymethyl)phenyl]-2-deoxy-3-O-triethylsilyl-D-arabino-1-hexenitol 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以77%的产率得到2',2'-bis(1,1-dimethylethyl)-4'a,7',8',8'a-tetrahydro-5,7-bis(phenylmethoxy)-8'-triethylsilyloxy-(1S,4'aR,7'S,8'R,8'aR)-spiro[isobenzofuran-1(3H),6'(4'H)-pyrano[3,2-d][1,3,2]dioxasilin]-7'-ol
  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：

  D-葡萄烯糖 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 吡啶 、 2,6-二甲基吡啶 、 水 、 叔丁基锂 、 二异丁基氢化铝 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 、 正戊烷 、 苯 为溶剂， 反应 11.5h， 生成 1,5-anhydro-4,6-O-[bis(1,1-dimethylethyl)silylene]-1-C-[2',4'-bis(phenylmethoxy)-6'-(hydroxymethyl)phenyl]-2-deoxy-3-O-triethylsilyl-D-arabino-1-hexenitol
  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.