(R)-4,4-dimethyl-3-(diphenylmethylsilyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-penten-5-al | 915377-81-0

• 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: (R)-4,4-dimethyl-3-(diphenylmethylsilyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-penten-5-al
• 英文别名: (3R)-2,2-dimethyl-3-[methyl(diphenyl)silyl]-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-4-enal
• CAS: 915377-81-0
• 化学式: C₂₆H₃₅BO₃Si
• 分子量: 434.459
• InChiKey: AGDISGGRDPEQOG-HSZRJFAPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.66
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  (R)-4,4-dimethyl-3-(diphenylmethylsilyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-penten-5-al 在 2-双环己基膦-2',6'-二甲氧基联苯 、 palladium diacetate 、 palladium on activated charcoal potassium phosphate 、 三氟甲磺酸三甲基硅酯 、 氢气 作用下， 以 乙醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 17.0h， 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 、 2-(methyldiphenylsilyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 catalyst:Pd(dba)2/R-1,1'-bina-2yl-P(3,5C₆H₃-Me₂)2 作用下， 以 甲苯 为溶剂， 以95%的产率得到(R)-4,4-dimethyl-3-(diphenylmethylsilyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-penten-5-al
  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.