(Z)-2-(dimethylphenylsilylmethylene)-3-methylbutanal | 398453-87-7

• 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: (Z)-2-(dimethylphenylsilylmethylene)-3-methylbutanal
• 英文别名: (2Z)-2-[[dimethyl(phenyl)silyl]methylidene]-3-methylbutanal
• CAS: 398453-87-7
• 化学式: C₁₄H₂₀OSi
• 分子量: 232.398
• InChiKey: BHUKTPPYRILQOX-ACCUITESSA-N

物化性质

• 沸点：
  299.1±23.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  (Z)-2-(dimethylphenylsilylmethylene)-3-methylbutanal 在 四丁基氟化铵 、 水 作用下， 以 二甲基亚砜 为溶剂， 以46%的产率得到2-benzyl-3-methylbutanal
  参考文献：
  名称：

  氟化物促进的有机硅化合物的重排：由1-炔烃合成新的2-（芳基甲基）醛。

  摘要：

  提出了基于芳基的1，2-阴离子重排的2-（芳基甲基）醛4的新方法。合成序列开始于末端乙炔5与芳基和杂芳基硅烷6的甲硅烷基甲酰化反应，然后用TBAF处理产物（Z）-1。描述了氟化物促进步骤的实验条件的优化，以及该方法的合成潜力。据报道，重排反应的可能机制表明氟离子被添加到β-甲硅烷基烯醛（Z）-1的芳基硅部分，随后芳基迁移到相邻的碳原子上。芳基和杂芳基取代基都可以重新排列而没有任何构型损失。

  DOI：

  10.1021/jo0351062
• 作为产物：
  描述：

  1-溴-3-甲基丁-1,2-二烯 、 alkaline earth salt of/the/ methylsulfuric acid 在 铑 、 均三甲苯 lithium aluminium tetrahydride 作用下， 以 甲苯 为溶剂， 25.0 ℃ 、1000.0 kPa 条件下， 反应 24.0h， 生成 (Z)-2-(dimethylphenylsilylmethylene)-3-methylbutanal
  参考文献：
  名称：

  Silylformylation of Chiral 1-Alkynes, Catalysed by Solvated Rhodium Atoms

  摘要：

  Solvated rhodium atoms, prepared by the metal vapour synthesis technique, promote the silylformylaton reaction of variously substituted alkynes (RRCH)-R-1-C-2(CH2)(n)C equivalent to CH, with catalytic activities comparable with and even higher than more common species such as Rh-4(CO)(12). Z-Silylalkenals are exclusively formed in high yields (60-95%) indicating syn addition both of CO and of the silane (Me2PhSiH) to the triple bond, The chemoselectivity of the process (silylformylation vs. hydrosilylation) is highly affected by the amount of catalyst employed (mmol of Rh species with respect to the alkyne reagent), by the steric requirements of the acetylenic substrates and by the hydrosilane/alkyne molar ratio. When optically active acetylenes are treated in the presence of Me2PhSiH under carbon monoxide pressure, the silylformylation reaction occurs with total retention of stereochemistry of the stereogenic centre, even if it is at the alpha -position of the unsaturated moiety, to afford enantiomerically enriched beta -silylalkenals.

  DOI：

  10.1002/1099-0690(200111)2001:22<4321::aid-ejoc4321>3.0.co;2-t

文献信息

• New synthesis of α-benzylaldehydes from 2-(dimethylphenylsilylmethylene)alkanals by fluoride promoted phenyl migration
  作者：Laura Antonella Aronica、Francesca Morini、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1016/s0040-4039(02)01178-4

  日期：2002.8

  α-Benzyl aldehydes are prepared from easily available β-silylalkenals and fluoride reagents, under mild experimental conditions; the reaction occurs instantaneously with almost quantitative yields. A plausible mechanism is suggested, which involves a 1,2-phenyl migration from the silicon to the adjacent carbon atom.

  在温和的实验条件下，由容易获得的β-甲硅烷基烯酮和氟化物试剂制得α-苄基醛。该反应瞬间发生，收率几乎定量。提出了一种可能的机理，该机理涉及1,2-苯基从硅迁移到相邻的碳原子。
• Silylformylation of Chiral 1-Alkynes, Catalysed by Solvated Rhodium Atoms
  作者：Laura Antonella Aronica、Silvia Terreni、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1002/1099-0690(200111)2001:22<4321::aid-ejoc4321>3.0.co;2-t

  日期：2001.11

  Solvated rhodium atoms, prepared by the metal vapour synthesis technique, promote the silylformylaton reaction of variously substituted alkynes (RRCH)-R-1-C-2(CH2)(n)C equivalent to CH, with catalytic activities comparable with and even higher than more common species such as Rh-4(CO)(12). Z-Silylalkenals are exclusively formed in high yields (60-95%) indicating syn addition both of CO and of the silane (Me2PhSiH) to the triple bond, The chemoselectivity of the process (silylformylation vs. hydrosilylation) is highly affected by the amount of catalyst employed (mmol of Rh species with respect to the alkyne reagent), by the steric requirements of the acetylenic substrates and by the hydrosilane/alkyne molar ratio. When optically active acetylenes are treated in the presence of Me2PhSiH under carbon monoxide pressure, the silylformylation reaction occurs with total retention of stereochemistry of the stereogenic centre, even if it is at the alpha -position of the unsaturated moiety, to afford enantiomerically enriched beta -silylalkenals.
• Fluoride-Promoted Rearrangement of Organo Silicon Compounds:  A New Synthesis of 2-(Arylmethyl)aldehydes from 1-Alkynes
  作者：Laura Antonella Aronica、Patrizio Raffa、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1021/jo0351062

  日期：2003.11.1

  A new approach to 2-(arylmethyl)aldehydes 4 based upon a 1,2-anionotropic rearrangement of an aryl group is presented. The synthetic sequence begins with a silylformylation reaction of terminal acetylenes 5 with aryl and heteroaryl silanes 6, followed by treatment of the products (Z)-1 with TBAF. The optimization of the experimental conditions of the fluoride-promoted step is described, together with

  提出了基于芳基的1，2-阴离子重排的2-（芳基甲基）醛4的新方法。合成序列开始于末端乙炔5与芳基和杂芳基硅烷6的甲硅烷基甲酰化反应，然后用TBAF处理产物（Z）-1。描述了氟化物促进步骤的实验条件的优化，以及该方法的合成潜力。据报道，重排反应的可能机制表明氟离子被添加到β-甲硅烷基烯醛（Z）-1的芳基硅部分，随后芳基迁移到相邻的碳原子上。芳基和杂芳基取代基都可以重新排列而没有任何构型损失。