(3-Methylbut-2-enoyl)triphenylsilane | 137122-51-1

• 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: (3-Methylbut-2-enoyl)triphenylsilane
• 英文别名: 3-Methyl-1-triphenylsilylbut-2-en-1-one
• CAS: 137122-51-1
• 化学式: C₂₃H₂₂OSi
• 分子量: 342.513
• InChiKey: DHPVQPAHKRNDGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3-Methylbut-2-enoyl)triphenylsilane 在 二乙醇胺 、 (-)-diisopinocamphenylborane chloride 作用下， 生成 (S)-3-Methyl-1-triphenylsilanyl-but-2-en-1-ol 、 (R)-1-(Triphenylsilyl)-3-methylbut-2-en-1-ol
  参考文献：
  名称：

  Thermal rearrangements of .alpha.-(acyloxy)silanes: formation of chiral precursors and migratory preference of silicon-based groups

  摘要：

  The asymmetric reduction of acylsilanes to chiral alpha-hydroxysilanes and the thermal rearrangement of the corresponding chiral alpha-acetoxysilanes was explored. IpcBCl reduces many acylsilanes in > 95% ee. The rate of the thermal rearrangement of the alpha-acetoxysilanes was dependent upon the substituents at both silicon and carbon. Evidence is presented to indicate there is electron deficiency at the alpha-carbon in the transition state. Migratory aptitudes follow those expected on the basis of the migrating group assuming an apical migratory group at a pentacoordinate silicon. A previously unreported hydrolytic transformation of a proposed acylsilyl hydride to a stable 1-sila-1,2-diol was observed.

  DOI：

  10.1021/jo00025a024
• 作为产物：
  描述：

  3-甲基巴豆酰氯 、 三苯基氯硅烷 生成 (3-Methylbut-2-enoyl)triphenylsilane
  参考文献：
  名称：

  Thermal rearrangements of .alpha.-(acyloxy)silanes: formation of chiral precursors and migratory preference of silicon-based groups

  摘要：

  The asymmetric reduction of acylsilanes to chiral alpha-hydroxysilanes and the thermal rearrangement of the corresponding chiral alpha-acetoxysilanes was explored. IpcBCl reduces many acylsilanes in > 95% ee. The rate of the thermal rearrangement of the alpha-acetoxysilanes was dependent upon the substituents at both silicon and carbon. Evidence is presented to indicate there is electron deficiency at the alpha-carbon in the transition state. Migratory aptitudes follow those expected on the basis of the migrating group assuming an apical migratory group at a pentacoordinate silicon. A previously unreported hydrolytic transformation of a proposed acylsilyl hydride to a stable 1-sila-1,2-diol was observed.

  DOI：

  10.1021/jo00025a024

文献信息

• Asymmetric Allylboration of Acylsilanes
  作者：John D. Buynak、Bolin Geng、Shinian Uang、J.Byron Strickland

  DOI：10.1016/s0040-4039(00)79945-x

  日期：1994.2

  Asymmetric allylboration of acylsilanes with B-allyldiisopinocampheylborane [(+)-Ipc2BAII] is highly substrate dependent, resulting in variable amounts of asymmetric induction. The determination of enantiomeric excess of the resulting highly hindered tertiary silylcarbinols was accomplished by reaction with diazaphospholidine 6 in the presence of a catalytic amount of methoxyacetic acid.

  酰基硅烷与B-烯丙基异硫代樟脑硼烷[（+）-Ipc 2 BAII]的不对称烯丙基硼化高度依赖于底物，导致可变数量的不对称诱导。在催化量的甲氧基乙酸的存在下，通过与二氮磷吡啶6反应来完成对所得的高度受阻的叔甲硅烷基甲醇的对映体过量的测定。