(E)-triisopropyl((2-isopropyl-1-phenylbut-2-en-1-yl)oxy)silane | 1223452-02-5

• 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: (E)-triisopropyl((2-isopropyl-1-phenylbut-2-en-1-yl)oxy)silane
• 英文别名: (E)-triisopropyl[(2-isopropyl-1-phenylbut-2-en-1-yl)oxy]silane
• CAS: 1223452-02-5
• 化学式: C₂₂H₃₈OSi
• 分子量: 346.629
• InChiKey: OODGFHFGYWUARP-UFFVCSGVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.52
• 重原子数：
  24.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  甲基異丙基乙炔 、 三异丙基硅烷 、 苯甲醛 在 bis(1,5-cyclooctadiene)nickel (0) 、 potassium tert-butylate 、 1,3-双-(2,6-二异丙基苯基)咪唑鎓氯化物 作用下， 以 四氢呋喃 为溶剂， 以78%的产率得到(E)-triisopropyl((2-isopropyl-1-phenylbut-2-en-1-yl)oxy)silane
  参考文献：
  名称：

  Regiocontrol in Catalytic Reductive Couplings through Alterations of Silane Rate Dependence

  摘要：

  Combinations of ligand, reducing agent, and reaction conditions have been identified that allow alteration in the rate- and regioselectivity-determining step of nickel-catalyzed aldehyde-alkyne reductive couplings. Whereas previously developed protocols involve metallacycle-forming oxidative cyclization as the rate-determining step, this study illustrates that the combination of large ligands, large silanes, and elevated reaction temperature alters the rate- and regiochemistry-determining step for one of the two possible product regioisomers. These modifications render metallacycle formation reversible for the minor isomer pathway, and sigma-bond metathesis of the metallacycle Ni-O bond with the silane reductant becomes rate limiting. The ability to tune regiocontrol via this alteration in reversibility of a key step allows highly regioselective outcomes that were not possible using previously developed methods.

  DOI：

  10.1021/ja511778a

文献信息

• A General Strategy for Regiocontrol in Nickel-Catalyzed Reductive Couplings of Aldehydes and Alkynes
  作者：Hasnain A. Malik、Grant J. Sormunen、John Montgomery

  DOI：10.1021/ja102262v

  日期：2010.5.12

  a broad range of couplings, without relying on substrate biases or directing effects. The complementary use of small cyclopropenylidene carbene ligands or highly hindered N-heterocyclic carbene ligands allows the regiochemical reversal with unbiased internal alkynes, aromatic internal alkynes, conjugated enynes, or terminal alkynes.

  已经开发出一种在醛-炔还原偶联中催化剂控制的区域选择性策略。该策略是第一个可以为广泛的耦合选择区域化学结果的策略，而不依赖于底物偏差或定向效应。小亚环丙烯卡宾配体或高度受阻的N-杂环卡宾配体的互补使用允许与无偏内炔、芳香内炔、共轭烯炔或末端炔进行区域化学逆转。