ethyl 4-[(4S)-3,3-dimethyl-4-phenylmethoxycyclopenten-1-yl]benzoate | 915377-93-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl 4-[(4S)-3,3-dimethyl-4-phenylmethoxycyclopenten-1-yl]benzoate
• CAS: 915377-93-4
• 化学式: C₂₃H₂₆O₃
• 分子量: 350.458
• InChiKey: LXTPLKDSEMROHP-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 4-[(4S)-3,3-dimethyl-4-phenylmethoxycyclopenten-1-yl]benzoate 在 palladium on activated charcoal 4-二甲氨基吡啶 、 氢气 、 N,N'-二环己基碳二亚胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 10.0h， 生成
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaboration of Allenes

  摘要：

  An enantioselective silaboration of allenes was achieved using an achiral silylborane in the presence of a palladium catalyst bearing a chiral monodentate phosphine ligand. (R)-2-Bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivities in the addition of (diphenylmethylsilyl)pinacolborane to the internal C=C bond of terminal allenes at 0 degrees C, giving the corresponding beta-borylallylsilanes in high yields with high enantiomeric excesses. The enantioselectivity depended on the bulkiness of substituents of allenes: the enantiomeric excesses were found to be 91-93% ee (R = tert- and sec-alkyl), 88-90% ee (R = aryl), and 80-82% ee (R = prim-alkyl and Me) at 0 degrees C. Perfect chirality transfer was observed in the intramolecular cyclization reactions of the functionalized allylsilanes, affording highly enantioenriched cyclic alkenylboranes, which underwent Suzuki-Miyaura coupling with aryl halides.

  DOI：

  10.1021/ja063934h
• 作为产物：
  描述：

  2,2-二甲基戊-3,4-二烯醛 在 2-双环己基膦-2',6'-二甲氧基联苯 、 (S)-联萘(3,5-二甲苯基)膦 、 palladium diacetate 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ potassium phosphate 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 97.0h， 生成 ethyl 4-[(4S)-3,3-dimethyl-4-phenylmethoxycyclopenten-1-yl]benzoate
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaboration of Allenes

  摘要：

  An enantioselective silaboration of allenes was achieved using an achiral silylborane in the presence of a palladium catalyst bearing a chiral monodentate phosphine ligand. (R)-2-Bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivities in the addition of (diphenylmethylsilyl)pinacolborane to the internal C=C bond of terminal allenes at 0 degrees C, giving the corresponding beta-borylallylsilanes in high yields with high enantiomeric excesses. The enantioselectivity depended on the bulkiness of substituents of allenes: the enantiomeric excesses were found to be 91-93% ee (R = tert- and sec-alkyl), 88-90% ee (R = aryl), and 80-82% ee (R = prim-alkyl and Me) at 0 degrees C. Perfect chirality transfer was observed in the intramolecular cyclization reactions of the functionalized allylsilanes, affording highly enantioenriched cyclic alkenylboranes, which underwent Suzuki-Miyaura coupling with aryl halides.

  DOI：

  10.1021/ja063934h

文献信息

• Palladium-Catalyzed Asymmetric Silaboration of Allenes
  作者：Toshimichi Ohmura、Hiroki Taniguchi、Michinori Suginome

  DOI：10.1021/ja063934h

  日期：2006.10.1

  An enantioselective silaboration of allenes was achieved using an achiral silylborane in the presence of a palladium catalyst bearing a chiral monodentate phosphine ligand. (R)-2-Bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivities in the addition of (diphenylmethylsilyl)pinacolborane to the internal C=C bond of terminal allenes at 0 degrees C, giving the corresponding beta-borylallylsilanes in high yields with high enantiomeric excesses. The enantioselectivity depended on the bulkiness of substituents of allenes: the enantiomeric excesses were found to be 91-93% ee (R = tert- and sec-alkyl), 88-90% ee (R = aryl), and 80-82% ee (R = prim-alkyl and Me) at 0 degrees C. Perfect chirality transfer was observed in the intramolecular cyclization reactions of the functionalized allylsilanes, affording highly enantioenriched cyclic alkenylboranes, which underwent Suzuki-Miyaura coupling with aryl halides.