tert-butyl-dimethyl-[(3E)-5-methylhexa-1,3-dien-2-yl]oxysilane | 198642-27-2

• 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: tert-butyl-dimethyl-[(3E)-5-methylhexa-1,3-dien-2-yl]oxysilane
• CAS: 198642-27-2
• 化学式: C₁₃H₂₆OSi
• 分子量: 226.434
• InChiKey: WSOZAWMBNCZVAT-MDZDMXLPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  、 tert-butyl-dimethyl-[(3E)-5-methylhexa-1,3-dien-2-yl]oxysilane 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 3-((tert-butyldimethylsilyl)oxy)-5-isopropyl-9,9-dimethyl-8,10-dioxa-1-thiaspiro[5.5]undec-3-ene-7,11-dione
  参考文献：
  名称：

  Mechanism and Regioselectivity of the Cycloaddition of Thiones Derived from Meldrum’s Acid, Malonates, or Other Dicarbonyls

  摘要：

  [GRAPHICS]Several alpha,alpha-dioxothiones were generated in situ and reacted with 1,3-dienes of varying electronic and steric properties. It was found that thiones 10a and 11a reacted well with electron-rich or electron-poor dienes and are complementary in their regioselectivities when steric effects are at play. The calculated preferred mechanistic pathway implies a thiiranium zwitterion intermediate.

  DOI：

  10.1021/jo800945y
• 作为产物：
  描述：

  (E)-5-甲基己-3-烯-2-酮 、 叔丁基二甲基氯硅烷 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 六甲基磷酰三胺 为溶剂， 反应 1.0h， 以93%的产率得到tert-butyl-dimethyl-[(3E)-5-methylhexa-1,3-dien-2-yl]oxysilane
  参考文献：
  名称：

  Mechanism and Regioselectivity of the Cycloaddition of Thiones Derived from Meldrum’s Acid, Malonates, or Other Dicarbonyls

  摘要：

  [GRAPHICS]Several alpha,alpha-dioxothiones were generated in situ and reacted with 1,3-dienes of varying electronic and steric properties. It was found that thiones 10a and 11a reacted well with electron-rich or electron-poor dienes and are complementary in their regioselectivities when steric effects are at play. The calculated preferred mechanistic pathway implies a thiiranium zwitterion intermediate.

  DOI：

  10.1021/jo800945y

文献信息

• Intramolecular C-H Insertion Reactions of Acetoxy Fischer Carbene Complexes
  作者：Kei Takeda、Yasushi Okamoto、Akemi Nakajima、Eiichi Yoshii、Toru Koizumi

  DOI：10.1055/s-1997-992

  日期：1997.10

  The reaction of 4-substituted 2-(t-butyldimethylsiloxy)-1,3-butadiene with acetoxy chromium Fischer carbene complexes afforded bicyclo[4.1.0]heptene derivative 3, 18, an intramolecular C-H insertion product of the initially formed Diels-Alder adduct 6. The role of the metal and the heteroatom ligand in the carbene complex, and of the substituent at 3-position in 6 on the C-H insertion has been examined.

  4 取代的 2-(叔丁基二甲基硅氧基)-1,3-丁二烯与乙酰氧基铬 Fischer 碳烯配合物反应生成了双环[4.1.0]庚烯衍生物 3，18，这是最初形成的 Diels-Alder 加合物 6 的分子内 C-H 插入产物。我们研究了碳烯配合物中金属和杂原子配体的作用，以及 6 中 3 位取代基在 C-H 插入过程中的作用。