4-trimethylsilyl-2-trimethylsilyloxypenta-2,3-diene | 82201-98-7

• 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: 4-trimethylsilyl-2-trimethylsilyloxypenta-2,3-diene
• CAS: 82201-98-7
• 化学式: C₁₁H₂₄OSi₂
• 分子量: 228.482
• InChiKey: NVPJYOKUXRFGMJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  4-trimethylsilyl-2-trimethylsilyloxypenta-2,3-diene 在 三乙胺 、 间氯过氧苯甲酸 、 zinc dibromide 作用下， 以 二氯甲烷 为溶剂， 反应 1.08h， 生成 4-甲基辛-3-烯-2-酮
  参考文献：
  名称：

  由β-硅烯酮和β-硅烯酮合成αβ-不饱和酮

  摘要：

  共轭加成，然后进行烷基化，溴化和去甲硅烷基溴化反应，使β-甲硅烷基酮（4）成为3 d 3-合成子（5）和β-甲硅烷基酮（6）成为2a 3 d 3-合成子（7）。

  DOI：

  10.1016/s0040-4020(01)93277-6
• 作为产物：
  描述：

  三甲基氯硅烷 、 4-三甲基硅基-3-丁炔-2-酮 、 甲基锂 在 copper(l) iodide 、 lithium iodide 作用下， 生成 4-trimethylsilyl-2-trimethylsilyloxypenta-2,3-diene
  参考文献：
  名称：

  NMR Spectroscopic Investigation of the Adducts Formed by Addition of Cuprates to Ynoates and Ynones: Alkenylcuprates or Allenolates?

  摘要：

  The adducts obtained by reaction of Me3CuLi . LiI, tBuCu(CN)Li, and tBu(2)CuLi . LiCN with ynoates and ynones were characterized by determination of their C-13 NMR chemical shifts and C-13, C-13 coupling constants. Alkenyl-copper adducts were formed from ynoates and Me2CuLi . LiI or tBuCu(CN)Li, whereas allenolates are obtained from ynoates and tBu(2)CuLi . LiCN, as well as from ynones and Me2CuLi . LiI. The transformations can therefore be regarded as carbocupration of an alkyne rather than a Michael addition. The equilibrium between alkenylcuprates and allenolates can be shifted towards lithium allenolates by addition of organolithium compounds. In the case of adducts formed from Me2CuLi . LiI, isomerization of cis- to trans-alkenylcuprates via the corresponding allenolate can be prevented by removal of LiI or by the use of THF as solvent. Whereas the protonation of alkenylcuprates to the corresponding alkenes proceeds stereospecifically, it is difficult to control the steric course of the protonation of allenolates. Addition of chlorotrimethylsilane to the adducts gives silyl ketene acetals or enol ethers in all cases.

  DOI：

  10.1002/(sici)1521-3765(19981002)4:10<2051::aid-chem2051>3.0.co;2-f

文献信息

• FLEMING, I.;PERRY, D. A., TETRAHEDRON, 1981, 37, N 23, 4027-4034
  作者：FLEMING, I.、PERRY, D. A.

  DOI：——

  日期：——
• The synthesis of αβ-unsaturated ketones from β-silylenones and β-silylynones
  作者：Ian Fleming、David A. Perry

  DOI：10.1016/s0040-4020(01)93277-6

  日期：——

  Conjugate addition, followed by alkylation, bromination and desilyl-bromination make the β-silylketone (4) an a3d3-synthon (5) and the β-silylynone (6) a 2a3d3-synthon (7).

  共轭加成，然后进行烷基化，溴化和去甲硅烷基溴化反应，使β-甲硅烷基酮（4）成为3 d 3-合成子（5）和β-甲硅烷基酮（6）成为2a 3 d 3-合成子（7）。
• NMR Spectroscopic Investigation of the Adducts Formed by Addition of Cuprates to Ynoates and Ynones: Alkenylcuprates or Allenolates?
  作者：Karolina Nilsson、Thomas Andersson、Christina Ullenius、Andreas Gerold、Norbert Krause

  DOI：10.1002/(sici)1521-3765(19981002)4:10<2051::aid-chem2051>3.0.co;2-f

  日期：1998.10.2

  The adducts obtained by reaction of Me3CuLi . LiI, tBuCu(CN)Li, and tBu(2)CuLi . LiCN with ynoates and ynones were characterized by determination of their C-13 NMR chemical shifts and C-13, C-13 coupling constants. Alkenyl-copper adducts were formed from ynoates and Me2CuLi . LiI or tBuCu(CN)Li, whereas allenolates are obtained from ynoates and tBu(2)CuLi . LiCN, as well as from ynones and Me2CuLi . LiI. The transformations can therefore be regarded as carbocupration of an alkyne rather than a Michael addition. The equilibrium between alkenylcuprates and allenolates can be shifted towards lithium allenolates by addition of organolithium compounds. In the case of adducts formed from Me2CuLi . LiI, isomerization of cis- to trans-alkenylcuprates via the corresponding allenolate can be prevented by removal of LiI or by the use of THF as solvent. Whereas the protonation of alkenylcuprates to the corresponding alkenes proceeds stereospecifically, it is difficult to control the steric course of the protonation of allenolates. Addition of chlorotrimethylsilane to the adducts gives silyl ketene acetals or enol ethers in all cases.