(1RS,4RS)-1-(dimethyl(phenyl)silyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-cyclohexene

• 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: (1RS,4RS)-1-(dimethyl(phenyl)silyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-cyclohexene
• 英文别名: dimethyl-phenyl-[(1S,4S)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-2-en-1-yl]silane
• 化学式: C₂₀H₃₁BO₂Si
• 分子量: 342.361
• InChiKey: ROZYQBXOMNMBMQ-SJLPKXTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.78
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,3-环己二烯 、 (二甲基苯硅烷基)硼酸频那醇酯 在 bis(acetylacetonate)nickel(II) 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 24.0h， 生成 (1RS,4RS)-1-(dimethyl(phenyl)silyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-cyclohexene 、 (1RS,4SR)-1-(dimethyl(phenyl)silyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-cyclohexene
  参考文献：
  名称：

  Stereoselective 1,4-Silaboration of 1,3-Dienes Catalyzed by Nickel Complexes

  摘要：

  The silicon-boron bond of (dimethylphenylsilyl)pinacolborane was stereoselectively added to acyclic 1,3-dienes in a 1,4-fashion to give (Z)4-boryl-1 -silyl-2-alkene derivatives in the presence of a Ni(0) catalyst generated from Ni(acac)(2) and diisobutylaluminum hydride, 1,4-Silaboration of cyclic 1,3-dienes required the use of cyclohexyldiphenylphosphine with the Ni(0) catalyst to afford cis-1-boryl-1-silyl-2-cycloalkene derivatives in high yields with high stereoselectivities.

  DOI：

  10.1021/ol990908y

文献信息

• Enantioselective Platinum-Catalyzed Silicon-Boron Addition to 1,3-Cyclohexadiene
  作者：Martin Gerdin、Christina Moberg

  DOI：10.1002/adsc.200505016

  日期：2005.5

  Silaboration of 1,3-cyclohexadiene in the presence of Pt(acac)2, DIBALH, and a phosphoramidite prepared from (S)-1,1′-bi-2-naphthol and diisopropylamine led to (1R,4S)-1-(dimethylphenylsilyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-cyclohexene with 70% ee. Chiral catalysts based on Ni gave no or essentially racemic product, whereas complexes containing Pd were inactive.

  在Pt（acac）2，DIBALH和由（S）-1,1'-bi-2-萘酚和二异丙胺制得的亚磷酰胺存在下1,1,3-环己二烯的硅烷化反应导致（1 R，4 S）-具有70％ee的1-（二甲基苯基甲硅烷基）-4-（4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基）-2-环己烯。基于Ni的手性催化剂不产生或基本上不产生外消旋产物，而含Pd的配合物则无活性。