4-(2-benzyloxy-phenyl)-4-(tert-butyldimethylsilanyloxy)-1-(1,4,5,6,8-pentamethoxy-naphthalen-2-yl)-butan-2-one | 1315340-94-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 4-(2-benzyloxy-phenyl)-4-(tert-butyldimethylsilanyloxy)-1-(1,4,5,6,8-pentamethoxy-naphthalen-2-yl)-butan-2-one
• 英文别名: 4-[Tert-butyl(dimethyl)silyl]oxy-1-(1,4,5,6,8-pentamethoxynaphthalen-2-yl)-4-(2-phenylmethoxyphenyl)butan-2-one
• CAS: 1315340-94-3
• 化学式: C₃₈H₄₈O₈Si
• 分子量: 660.88
• InChiKey: REOIYPMVHAYLEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.73
• 重原子数：
  47
• 可旋转键数：
  16
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  81.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4-(2-benzyloxy-phenyl)-4-(tert-butyldimethylsilanyloxy)-1-(1,4,5,6,8-pentamethoxy-naphthalen-2-yl)-butan-2-one 在 ammonium cerium (IV) nitrate 作用下， 以 水 、 乙腈 为溶剂， 反应 0.17h， 以65%的产率得到6-[4-(2-benzyloxy-phenyl)-4-(tert-butyldimethylsilanyloxy)-2-oxo-butyl]-2,5,8-trimethoxy-[1,4]naphthoquinone
  参考文献：
  名称：

  Alternative Spiroketalization Methods toward Purpuromycin: A Hemiketal Conjugate Addition Strategy and Use of an Electron-Rich Isocoumarin Precursor

  摘要：

  Two methods are presented that were designed to circumvent the persistent problem of benzofuran formation and instead yield a spiroketal of the rubromycin family type. First, using an alternative disconnection, a hemiketal conjugate addition to a naphthaquinone electrophile was investigated. Synthesis of the requisite electrophile provided insight into the selective oxidation and functionalization of the naphthalene portion. Second, the electronic features of the isocoumarin ring system were adjusted, and the corresponding reactivity further supports the hypothesis that electron-rich isocoumarins are capable of spiroketalization. Robust, flexible syntheses from simple precursors were developed that allowed multiple reduced isocoumarins to be generated. Combined, the data presented herein give insight into the sensitivities of this family and illuminate other potential methods of spiroketalization. In addition, the convergent assembly of substrates containing different naphthaquinone and isocoumarin subunits highlights the utility of our 1,3-dipolar cycloaddition approach to generate analogs of these structures for SAR, as well as chemical reactivity studies.

  DOI：

  10.1021/jo200398v
• 作为产物：
  描述：

  1,2,4,5,8-pentamethoxynaphthalene 在 ammonium acetate 、 水 、 氢气 、 硼酸 、 异氰酸苯酯 、 三乙胺 、 三氯氧磷 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 氯仿 、 异氰酸苯酯 、 苯 为溶剂， 反应 80.9h， 生成 4-(2-benzyloxy-phenyl)-4-(tert-butyldimethylsilanyloxy)-1-(1,4,5,6,8-pentamethoxy-naphthalen-2-yl)-butan-2-one
  参考文献：
  名称：

  Alternative Spiroketalization Methods toward Purpuromycin: A Hemiketal Conjugate Addition Strategy and Use of an Electron-Rich Isocoumarin Precursor

  摘要：

  Two methods are presented that were designed to circumvent the persistent problem of benzofuran formation and instead yield a spiroketal of the rubromycin family type. First, using an alternative disconnection, a hemiketal conjugate addition to a naphthaquinone electrophile was investigated. Synthesis of the requisite electrophile provided insight into the selective oxidation and functionalization of the naphthalene portion. Second, the electronic features of the isocoumarin ring system were adjusted, and the corresponding reactivity further supports the hypothesis that electron-rich isocoumarins are capable of spiroketalization. Robust, flexible syntheses from simple precursors were developed that allowed multiple reduced isocoumarins to be generated. Combined, the data presented herein give insight into the sensitivities of this family and illuminate other potential methods of spiroketalization. In addition, the convergent assembly of substrates containing different naphthaquinone and isocoumarin subunits highlights the utility of our 1,3-dipolar cycloaddition approach to generate analogs of these structures for SAR, as well as chemical reactivity studies.

  DOI：

  10.1021/jo200398v

文献信息

• Alternative Spiroketalization Methods toward Purpuromycin: A Diketone Approach To Prevent Benzofuran Formation
  作者：Andrew N. Lowell、Michael W. Fennie、Marisa C. Kozlowski

  DOI：10.1021/jo200399z

  日期：2011.8.19

  The central portion of purpuromycin has been assembled via a classical spiroketalization reaction. Key to promoting this reaction mode versus benzofuran formation was the oxidation state of the spiroketal core. With a higher oxidation state, even the electron-deficient isocoumarin found in purpuromycin could be employed directly in the spiroketalization. The two halves of the spiroketalization precursor were joined via a nitrile oxide/styrene 1,3-dipolar cycloaddition. A very mild selenium dioxide oxidation was used to introduce the required oxidation state of the spiroketal core.
• Alternative Spiroketalization Methods toward Purpuromycin: A Hemiketal Conjugate Addition Strategy and Use of an Electron-Rich Isocoumarin Precursor
  作者：Rakeshwar Bandichhor、Andrew N. Lowell、Marisa C. Kozlowski

  DOI：10.1021/jo200398v

  日期：2011.8.19

  Two methods are presented that were designed to circumvent the persistent problem of benzofuran formation and instead yield a spiroketal of the rubromycin family type. First, using an alternative disconnection, a hemiketal conjugate addition to a naphthaquinone electrophile was investigated. Synthesis of the requisite electrophile provided insight into the selective oxidation and functionalization of the naphthalene portion. Second, the electronic features of the isocoumarin ring system were adjusted, and the corresponding reactivity further supports the hypothesis that electron-rich isocoumarins are capable of spiroketalization. Robust, flexible syntheses from simple precursors were developed that allowed multiple reduced isocoumarins to be generated. Combined, the data presented herein give insight into the sensitivities of this family and illuminate other potential methods of spiroketalization. In addition, the convergent assembly of substrates containing different naphthaquinone and isocoumarin subunits highlights the utility of our 1,3-dipolar cycloaddition approach to generate analogs of these structures for SAR, as well as chemical reactivity studies.