2-[(trimethylsilyl)methyl]benzyl methyl carbonate | 909792-50-3

• 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: 2-[(trimethylsilyl)methyl]benzyl methyl carbonate
• 英文别名: methyl 2-[(trimethylsilyl)methyl]benzyl carbonate；methyl [2-{(trimethylsilyl)methyl}phenyl]methyl carbonate；o-[(trimethylsilyl)methyl]benzyl carbonate；Methyl [2-(trimethylsilylmethyl)phenyl]methyl carbonate
• CAS: 909792-50-3
• 化学式: C₁₃H₂₀O₃Si
• 分子量: 252.386
• InChiKey: CLRUFAUBLMMGPF-UHFFFAOYSA-N

物化性质

• 沸点：
  298.9±28.0 °C(Predicted)
• 密度：
  1.008±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.39
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  2-[(trimethylsilyl)methyl]benzyl methyl carbonate 、 2-环己烯-1-酮 在 三(4-甲氧基-3,5-二甲基苯基)膦 、 allyl(cyclopentadiene)palladium(II) 作用下， 以 二甲基亚砜 为溶剂， 反应 48.0h， 以50%的产率得到trans-3,4,4a,9,9a,10-hexahydro-1(2H)-anthracenone
  参考文献：
  名称：

  钯催化邻（甲硅烷基甲基）苄基碳酸酯与烯烃的[4+2]环加成反应的改进

  摘要：

  钯配合物由 Pd(η 3-C3H5)Cp 和三（4-甲氧基-3,5-二甲基苯基）膦原位生成，催化邻（甲硅烷基甲基）苄基碳酸酯与烯烃。苄酯与巴豆酸甲酯的反应以84%的收率和2%的催化剂负载得到3-甲基四氢化萘-2-羧酸甲酯。

  DOI：

  10.1055/s-0034-1379014
• 作为产物：
  描述：

  2-[(trimethylsilyl)methyl]benzyl alcohol 、 氯甲酸甲酯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 以99%的产率得到2-[(trimethylsilyl)methyl]benzyl methyl carbonate
  参考文献：
  名称：

  Palladium-Catalyzed Formal [4+2] Cycloaddtion of o-Xylylenes with Olefins

  摘要：

  o-(Silylmethyl)benzylic carbonates reacted with various conjugated olefins in the presence of the palladium catalyst, which was generated in situ from Pd(eta(3)-C3H5)Cp and 1,2-bis(diphenylphosphino)ethane (DPPE). The reaction provided 2- and/or 3-substituted tetralins in good yield. The catalytic reaction described here is equivalent to the [4+2] cycloaddition of o-xylylenes with dienophiles.

  DOI：

  10.1021/ja070012l

文献信息

• Palladium-Catalyzed [4 + 2] Cycloaddition of <i>o</i>-(Silylmethyl)benzyl Esters with Ketones: An Equivalent to Oxo-Diels−Alder Reaction of <i>o</i>-Xylylenes
  作者：Satoshi Ueno、Masakazu Ohtsubo、Ryoichi Kuwano

  DOI：10.1021/ol101792a

  日期：2010.10.1

  o-(Silylmethyl)benzyl carbonates reacted with various electron-deficient ketones in the presence of a palladium catalyst, affording the [4 + 2] cycloaddition products, isochromanes, in high yields. The palladium-catalyzed cycloaddition is equivalent to the oxo-Diels−Alder reaction of o-xylylene with ketones. The regioselectivities were extraordinarily affected by the structures of the o-xylylene precursors

  在钯催化剂的存在下，邻-（甲硅烷基甲基）苄基碳酸酯与各种缺电子的酮反应，以高收率提供了[4 + 2]环加成产物异色烷。钯催化的环加成反应相当于邻二甲苯基与酮的oxo-Diels-Alder反应。区域选择性特别受邻二甲苯前体和酮的结构影响。异常的区域化学反应可能在催化反应中支持两个竞争性反应途径。
• 2-[(Trimethylsilyl)methyl]benzyl Methanesulfonates: Useful Precursors for the Generation of o-Quinodimethanes
  作者：Hiroshi Sano、Hidenori Shirakawa

  DOI：10.1055/s-0033-1341238

  日期：——

  2-[(Trimethylsilyl)methyl]benzyl methanesulfonates react with potassium fluoride in the presence of a catalytic amount of 18-crown-6 at room temperature to give o-quinodimethanes, which are trapped with electron-deficient olefins to afford [4+2] cycloadducts in good yields.
• [4+2] Cycloaddition of <i>o</i>-Xylylenes with Imines Using Palladium Catalyst
  作者：Satoshi Ueno、Masakazu Ohtsubo、Ryoichi Kuwano

  DOI：10.1021/ja905988e

  日期：2009.9.16

  The cycloaddition of o-(silylmethyl)benzylic carbonates with imines proceeded in the presence of the Pd(eta(3)-C3H5)Cp-DPPPent catalyst, affording the tetrahydroisoquinolines in good to high yields. The reaction rate was remarkably increased by a fluoride additive. In the catalytic cycloaddition, the palladium(0) reacted with the benzylic substrate to form 2-palladaindane, which works as an o-xylylene equivalent. The catalytic reaction is equivalent to the hetero-Diets-Alder reaction of o-xylylene with imines.