1,5-anhydro-4,6-O-[bis(1,1-dimethylethyl)silylene]-2-deoxy-1-C-(hydroxydimethylsilyl)-3-O-(triethylsilyl)-D-arabino-1-hexenitol | 934243-66-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,5-anhydro-4,6-O-[bis(1,1-dimethylethyl)silylene]-2-deoxy-1-C-(hydroxydimethylsilyl)-3-O-(triethylsilyl)-D-arabino-1-hexenitol
• 英文别名: [(4aR,8R,8aR)-2,2-ditert-butyl-6-[hydroxy(dimethyl)silyl]-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3,2]dioxasilin-8-yl]oxy-triethylsilane
• CAS: 934243-66-0
• 化学式: C₂₂H₄₆O₅Si₃
• 分子量: 474.861
• InChiKey: HNDDAWCFZAHLCP-GGPKGHCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.85
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,5-anhydro-4,6-O-[bis(1,1-dimethylethyl)silylene]-2-deoxy-1-C-(hydroxydimethylsilyl)-3-O-(triethylsilyl)-D-arabino-1-hexenitol 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 二异丁基氢化铝 、 sodium t-butanolate 作用下， 以 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 5.5h， 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
• 作为产物：
  描述：

  D-葡萄烯糖 在 [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 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 、 正戊烷 、 苯 为溶剂， 反应 6.0h， 生成 1,5-anhydro-4,6-O-[bis(1,1-dimethylethyl)silylene]-2-deoxy-1-C-(hydroxydimethylsilyl)-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、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.