dimethyl 10,13-bis((R)-2-(benzoyloxy)propyl)-1,7,9,14-tetramethoxy-8,15-bis(triisopropylsilyloxy)dinaphtho[2,1-d:1',2'-f][1,3]dioxepine-2,6-dicarboxylate

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: dimethyl 10,13-bis((R)-2-(benzoyloxy)propyl)-1,7,9,14-tetramethoxy-8,15-bis(triisopropylsilyloxy)dinaphtho[2,1-d:1',2'-f][1,3]dioxepine-2,6-dicarboxylate
• 英文别名: dimethyl 5,21-bis[(2R)-2-benzoyloxypropyl]-6,9,17,20-tetramethoxy-7,19-bis[tri(propan-2-yl)silyloxy]-12,14-dioxapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3(8),4,6,9,16,18(23),19,21-decaene-10,16-dicarboxylate
• 化学式: C₆₇H₈₆O₁₆Si₂
• 分子量: 1203.58
• InChiKey: GBOWFVRQUYLSIR-OCQXTOTRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.68
• 重原子数：
  85
• 可旋转键数：
  28
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  dimethyl 10,13-bis((R)-2-(benzoyloxy)propyl)-1,7,9,14-tetramethoxy-8,15-bis(triisopropylsilyloxy)dinaphtho[2,1-d:1',2'-f][1,3]dioxepine-2,6-dicarboxylate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 dimethyl 5,21-bis[(2R)-2-benzoyloxypropyl]-7,19-dihydroxy-6,9,17,20-tetramethoxy-12,14-dioxapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3(8),4,6,9,16,18(23),19,21-decaene-10,16-dicarboxylate
  参考文献：
  名称：

  Perylenequinone Natural Products: Evolution of the Total Synthesis of Cercosporin

  摘要：

  The evolution of the First total synthesis of perylenequinone cercosporin is described. The key features developed during these efforts include a biscuprate epoxide alkylation, installation of the methylidene acetal, palladium-catalyzed O-arylation, and C3,C3'-decarbonylation. Due to the rapid atropisomerization of the helical axis of cercosporin (at 37 degrees C), the sequencing of these transformations was critical. To this end, the developed protocol enabled the formation of a key advanced intermediate oil preparative scale absent any atropisomerization. Furthermore, the O-arylation proved to be general, and the strategy was used in an improved synthesis of a helical chiral perylenequinone structure.

  DOI：

  10.1021/jo9013854
• 作为产物：
  描述：

  溴氯甲烷 、 dimethyl 7,7'-bis((R)-2-(benzoyloxy)propyl)-2,2'-dihydroxy-4,4',6,6'-tetramethoxy-5,5'-bis(triisopropylsilyloxy)-1,1'-binaphthyl-3,3'-dicarboxylate 在 异丙基溴化镁 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 以73%的产率得到dimethyl 10,13-bis((R)-2-(benzoyloxy)propyl)-1,7,9,14-tetramethoxy-8,15-bis(triisopropylsilyloxy)dinaphtho[2,1-d:1',2'-f][1,3]dioxepine-2,6-dicarboxylate
  参考文献：
  名称：

  Perylenequinone Natural Products: Evolution of the Total Synthesis of Cercosporin

  摘要：

  The evolution of the First total synthesis of perylenequinone cercosporin is described. The key features developed during these efforts include a biscuprate epoxide alkylation, installation of the methylidene acetal, palladium-catalyzed O-arylation, and C3,C3'-decarbonylation. Due to the rapid atropisomerization of the helical axis of cercosporin (at 37 degrees C), the sequencing of these transformations was critical. To this end, the developed protocol enabled the formation of a key advanced intermediate oil preparative scale absent any atropisomerization. Furthermore, the O-arylation proved to be general, and the strategy was used in an improved synthesis of a helical chiral perylenequinone structure.

  DOI：

  10.1021/jo9013854

文献信息

• Perylenequinone Natural Products: Evolution of the Total Synthesis of Cercosporin
  作者：Barbara J. Morgan、Carol A. Mulrooney、Marisa C. Kozlowski

  DOI：10.1021/jo9013854

  日期：2010.1.1

  The evolution of the First total synthesis of perylenequinone cercosporin is described. The key features developed during these efforts include a biscuprate epoxide alkylation, installation of the methylidene acetal, palladium-catalyzed O-arylation, and C3,C3'-decarbonylation. Due to the rapid atropisomerization of the helical axis of cercosporin (at 37 degrees C), the sequencing of these transformations was critical. To this end, the developed protocol enabled the formation of a key advanced intermediate oil preparative scale absent any atropisomerization. Furthermore, the O-arylation proved to be general, and the strategy was used in an improved synthesis of a helical chiral perylenequinone structure.