[(3,3-dimethylbut-1-en-2-yl)oxy]dimethylphenylsilane | 65335-66-2

• 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: [(3,3-dimethylbut-1-en-2-yl)oxy]dimethylphenylsilane
• 英文别名: [(3,3-Dimethylbut-1-en-2-yl)oxy](dimethyl)phenylsilane；3,3-dimethylbut-1-en-2-yloxy-dimethyl-phenylsilane
• CAS: 65335-66-2
• 化学式: C₁₄H₂₂OSi
• 分子量: 234.414
• InChiKey: DIBKSZIQWLNSOH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  频哪酮 、 二甲基苯基硅烷 在 C₂₈H₃₅PRuS⁽¹⁺⁾*C₃₃H₁₅BF₂₃^(1-) 作用下， 以 正己烷 为溶剂， 反应 0.08h， 以90%的产率得到[(3,3-dimethylbut-1-en-2-yl)oxy]dimethylphenylsilane
  参考文献：
  名称：

  Base-Free Dehydrogenative Coupling of Enolizable Carbonyl Compounds with Silanes

  摘要：

  A dehydrogenative coupling between enolizable carbonyl compounds and equimolar amounts of triorganosilanes catalyzed by a tethered ruthenium complex with a Ru-S bond is reported. The complex Is assumed to fulfill a dual role by activating the Si-H bond to release a silicon electrophile and by abstracting an a-proton from the intermediate silylcarboxonium ion, only liberating dihydrogen as the sole byproduct. Reaction rates are exceedingly high at room temperature with very low loadings of the ruthenium catalyst.

  DOI：

  10.1021/ol301089r

文献信息

• Re–Silane complexes as frustrated lewis pairs for catalytic hydrosilylation
  作者：Caleb A. Brown、Michael Abrahamse、Elon A. Ison

  DOI：10.1039/d0dt02084b

  日期：——

  concentration of an activated silane adduct which is the species responsible for catalytic turnover. A similar mechanism was found for both cationic and neutral Re(III) species. Further, it was shown by tuning the electrophilicity of the rhenium catalysts, conditions can be found that would enable the catalytic hydrosilylation of ketone and nitrile substrates that were unreactive in previously reported

  通过DFT（B3PW91-D3）计算了M（C 6 F 5）3（M = B，Al和Ga）对羰基底物的催化氢化硅烷化的途径，结果表明，在Al试剂的情况下，羰基底物不可逆地结合，并通过生成稳定的羰基加合物来抑制催化作用。相反，B（C 6 F 5）3的降低的亲电性不利于羰基底物的结合，并增加了活化的硅烷加合物的浓度，后者是引起催化转化的物质。发现阳离子和中性Re（III）的物种。此外，通过调节the催化剂的亲电性表明，发现了能够使酮和腈底物催化氢化硅烷化的条件，这些酮和腈底物在先前报道的系统中没有反应性。因此，这项工作中提出的机理为新催化体系的设计奠定了基础。