| 1265032-57-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• CAS: 1265032-57-2
• 化学式: C₂₁H₂₃NOSi
• 分子量: 333.505
• InChiKey: QHEGKMYNUYKSNI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  24.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  12.47
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 以24 mg的产率得到4-(二甲氨基)苄醇
  参考文献：
  名称：

  带有 PBP 配体的镍配合物催化羰基化合物的氢化硅烷化

  摘要：

  已经使用由二膦基硼基配体 (PBP) 支撑的镍钳氢化物复合物研究了酮和醛的有效催化氢化硅烷化。发现配体骨架内硼基的存在对观察到的酮的催化活性与相关的钳系统相比具有有益的影响。对反应机理的分析允许通过将羰基部分插入 Ni-H 键来合成和表征醇镍衍生物。结合实验和理论分析 (DFT) 支持这样一种反应机制，即首先形成醇盐配合物，然后与硅烷反应释放相应的甲硅烷基醚并再生催化剂。

  DOI：

  10.1002/ejic.202100425
• 作为产物：
  描述：

  二苯基硅烷 、 对二甲氨基苯甲醛 在 iron(II) bis(trimethylsilyl)amide 作用下， 以 氘代苯 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  简单酰胺催化剂[Fe {N（SiMe3）2} 2]对羰基化合物进行有效的氢硅烷化。

  摘要：

  保持简单：在标题络合物的存在下，多种酮和两个醛在温和条件下进行有效的氢化硅烷化（参见方案； R，R'= H，烷基，芳基）。在某些情况下，催化剂负载量仅为0.01-0.03 mol％就足够了。该催化剂可为酮的氢化硅烷化提供一种简单，经济高效且对环境无害的替代方法。

  DOI：

  10.1002/anie.201005055

文献信息

• Facile Si–H bond activation and hydrosilylation catalysis mediated by a nickel–borane complex
  作者：Samantha N. MacMillan、W. Hill Harman、Jonas C. Peters

  DOI：10.1039/c3sc52626g

  日期：——

  Metal–borane complexes are emerging as promising systems for study in the context of bifunctional catalysis. Herein we describe diphosphineborane nickel complexes that activate Si–H bonds and catalyze the hydrosilylation of aldehydes. Treatment of [MesDPBPh]Ni (1) ([MesDPBPh] = MesB(o-Ph2PC6H4)2) with organosilanes affords the complexes [MesDPBPh](μ-H)NiE (E = SiH2Ph (3), SiHPh2 (4)). Complex 4 is in solution equilibrium with 1 and the thermodynamic and kinetic parameters of their exchange have been characterized by NMR spectroscopy. Complex 1 is a catalyst for the hydrosilylation of a range of para-substituted benzaldehydes. Mechanistic studies on this reaction via multinuclear NMR spectroscopy are consistent with the intermediacy of a borohydrido-Ni-siloxyalkyl species.

  金属硼烷配合物正在成为双功能催化领域有前景的研究系统。在此，我们描述了二膦硼烷镍配合物，其可激活 Si–H 键并催化醛的氢化硅烷化。用有机硅烷处理 [MesDPBPh]Ni (1) ([MesDPBPh] = MesB(o-Ph2PC6H4)2) 得到络合物 [MesDPBPh](μ-H)NiE (E = SiH2Ph (3), SiHPh2 (4))。配合物 4 与 1 处于溶液平衡状态，并且它们交换的热力学和动力学参数已通过核磁共振波谱进行了表征。配合物 1 是一系列对位取代苯甲醛氢化硅烷化的催化剂。通过多核核磁共振波谱对该反应的机理研究与硼氢化-Ni-甲硅烷氧基烷基物质的中间作用一致。
• Iron-Catalyzed Hydrosilylation of Aldehydes and Ketones under Solvent-Free Conditions
  作者：Francis S. Wekesa、Renzo Arias-Ugarte、Lydia Kong、Zachary Sumner、Gregory P. McGovern、Michael Findlater

  DOI：10.1021/acs.organomet.5b00630

  日期：2015.10.26

  Exposure of aldehyde or ketone to 1 mol % BIAN-Fe(C7H8) complex in the presence of diphenyl silane affords the corresponding protected alcohol in excellent yields, under mild reaction conditions. Aldehydes and ketones are reduced cleanly in the presence of a broad range of functional groups under solvent-free conditions.
• E–H Bond Activations and Hydrosilylation Catalysis with Iron and Cobalt Metalloboranes
  作者：Mark A. Nesbit、Daniel L. M. Suess、Jonas C. Peters

  DOI：10.1021/acs.organomet.5b00530

  日期：2015.10.12

  An exciting challenge in transition metal catalyst design is to explore whether earth-abundant base metals such as Fe, Co, and Ni can mediate two-electron reductive transformations that their precious metal counterparts (e.g., Ru, Rh, Ir, and Pd) are better known to catalyze. Organometallic metalloboranes are an interesting design concept in this regard because they can serve as organometallic frustrated Lewis pairs. To build on prior studies with nickel metalloboranes featuring the DPB and (DPBMes)-D-Ph ligands in the context of H-2 and slime activation and catalysis (DPB = bis(o-diisopropylphosphinophenyl)phenylborane, (DPBMes)-D-Ph = bis (o-diphenylphosphinophenyl)mesitylborane), we now explore the reactivity of iron, [(DPB)Fe](2)(N-2), 1, and cobalt, (DPB)Co(N-2), 2, metalloboranes toward a series of substrates with E-H bonds (E = O, S, C, N) including phenol, thiophenol, benzo[h]quinoline, and 8-aminoquinoline. In addition to displaying high stoichiometric E-H bond activation reactivity, complexes 1 and 2 prove to be more active catalysts for the hydrosilylation of ketones and aldehydes with diphenylsilane relative to ((DPBMes)-D-Ph)Ni. Indeed, 2 appears to be the most active homogeneous cobalt catalyst reported to date for the hydrosilylation of acetophenone under the conditions studied.