Triethyl-(4-isopropylbenzyloxy)-silan | 53172-95-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: Triethyl-(4-isopropylbenzyloxy)-silan
• 英文别名: triethyl((4-isopropylbenzyl)oxy)silane；p-Isopropylbenzyloxy-triaethylsilan
• CAS: 53172-95-5
• 化学式: C₁₆H₂₈OSi
• 分子量: 264.483
• InChiKey: GCASZBTWBSZMAN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.33
• 重原子数：
  18.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  Triethyl-(4-isopropylbenzyloxy)-silan 生成 α-Hydroxy-α-triaethylsilyl-p-isopropyltoluol
  参考文献：
  名称：

  New anionic rearrangements. XVII. 1,2-Anionic rearrangements from oxygen to carbon in benzyloxyorganosilanes and benzyloxyorganogermanes

  摘要：

  DOI：

  10.1021/ja00817a030
• 作为产物：
  描述：

  三乙基硅烷 、 4-异丙基苯甲醇 在 acetonitrile;iridium(3+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;2-phenylpyridine;tetrakis[3,5-bis(trifluoromethyl)phenyl]boranuide 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.02h， 以100%的产率得到Triethyl-(4-isopropylbenzyloxy)-silan
  参考文献：
  名称：

  被困的Ir（III）硅烷催化中间体中供体-受体（Ir–H）→SiR3相互作用的证据

  摘要：

  The ionic iridacycle [(2-phenylenepyridine-kappa N,kappa C)-IrCp*(NCMe)][BArF24] ([2][BArF24]) displays a remarkable capability to catalyze the O-dehydrosilylation of alcohols at room temperature (0.4 x 10(3) < TON < 10(3), 8 x 10(3) < TOFi < 1.9 x 10(5) h(-1) for primary alcohols) that is explained by its exothermic reaction with Et3SiH, which affords the new cationic hydrido-Ir(III)-silylium species [3][BArF24]. Isothermal calorimetric titration (ITC) indicates that the reaction of [2][BArF24] with Et3SiH requires 3 equiv of the latter and releases an enthalpy of -46 kcal/mol in chlorobenzene. Density functional theory (DFT) calculations indicate that the therrnochemistry of this reaction is largely dominated by the concomitant bis-hydrosilylation of the released MeCN ligand. Attempts to produce [3][BF4] and [3][OTf] salts resulted in the formation of a known neutral hydrido-iridium(III) complex, i.e. 4, and the release of Et3SiF and Et3SiOTf, respectively. In both cases formation of the cationic p-hydrido-bridged bis-iridacyclic complexes [5][BF4] and [5][OTf], respectively, was observed. The structure of [5][OTf] was established by X-ray diffraction analysis. Conversion of [3] [BArF24] into 4 upon reaction with either 4-N,N-dimethylaminopyridine or [nBu(4)][OTf] indicates that the Ir center holds a +III formal oxidation state and that the Et3Si+ moiety behaves as a Z-type ligand according to Green's formalism. [3][BArF24], which was trapped and structurally characterized and its electronic structure investigated by state-of-the-art DFT methods (DFT-D, EDA, ETS-NOCV, QTAIM, ELF, NCI plots and NBO), displays the features of a cohesive hydridoiridium(III)-> silylium donor-acceptor complex. This study suggests that the fate of [3](+) in the O-dehydrosilylation of alcohols is conditioned by the nature of the associated counteranion and by the absence of Lewis base in the medium capable of irreversibly capturing the silylium species.

  DOI：

  10.1021/acs.organomet.6b00248

文献信息

• Hydrosilylation of Carbonyls Catalyzed by Hydridoborenium Borate Salts: Lewis Acid Activation and Anion Mediated Pathways
  作者：Sandeep Rawat、Mamta Bhandari、Vishal Kumar Porwal、Sanjay Singh

  DOI：10.1021/acs.inorgchem.0c00646

  日期：2020.5.18

  multinuclear NMR measurements for catalysts 1 and 2. The combined effect of carbonyl activation via the Lewis acidic hydridoborenium cation and the hydridic nature of the borate counteranion in 1 makes it a more efficient catalyst in comparison to that of carbonyl activation via the predominant Lewis acid activation pathway operating with catalyst 2. The catalytic cycle of 1 showed hydride transfer from

  由双（膦酰氨基）酰胺配体支撑的电子不饱和三配位氢硼阳离子[LBH] + [HB（C6F5）3]-（1）和[LBH] + [B（ ）4]-（2），被发现是在温和的反应条件下（L = [（2,4,6-Me3C6H2N）P（Ph2）} 2N]氢化一系列脂肪族和芳香族醛和酮的出色催化剂。通过对催化剂1和2的原位多核NMR测量，监测了PhCHO硅氢加氢反应的催化循环的关键步骤。1中路易斯酸氢硼化硼阳离子对羰基的活化作用与硼酸抗衡阴离子的氢化性质共同作用使其成为一种与通过主要的路易斯酸活化途径与催化剂2进行羰基活化相比，催化剂更有效。1的催化循环显示氢化物在第一步中从硼酸盐部分[HB（ ）3]-转移到PhCHO，形成[PhCH2-OB（ ）3]-，随后与Et3SiH进行σ键易位。产品为PhCH2-O-SiEt3。量子化学计算也支持1的硼酸根阴离子介导的机理。相反，由2催化的反应主要
• Cobalt Nanoparticles Formed upon Reaction of Cp*Co(III) Metallacycles with Na[BHEt ₃ ] Show Catalytic Activity in the Hydrosilylation of Aryl Ketones, Aldehydes and Nitriles
  作者：Carmen Antuña‐Hörlein、Fule Wu、Christophe Deraedt、Corinne Bouillet、Jean‐Pierre Djukic

  DOI：10.1002/ejic.202200563

  日期：2023.2.17

  The treatment of a cobaltacycle with Na[BHEt3] produces Co nanoparticles that are active as catalyst for the hydrosilylation of aromatic aldehydes, ketones and nitriles.

  用 Na[BHEt 3 ]处理钴环会产生 Co 纳米颗粒，其作为芳香醛、酮和腈的氢化硅烷化的催化剂具有活性。
• BICAAC-Derived Covalent and Cationic Ir(I) Complexes: Application of Ir(BICAAC)Cl(COD) Complexes as Catalysts for Transfer Hydrogenation and Hydrosilylation Reactions
  作者：Mandeep Kaur、Manu Adhikari、Krishna K. Manar、Yuvraj Yogesh、Darsana Prakash、Sanjay Singh

  DOI：10.1021/acs.inorgchem.3c01914

  日期：2024.1.22

  (Me/iPrBICAAC) upon reaction with [IrCl(COD)]2 smoothly afford mononuclear Ir(I) complexes that have been spectroscopically and structurally characterized. These complexes exhibit good catalytic activity for transfer hydrogenation (TH) of 4-chlorobenzaldehyde using isopropyl alcohol (iPrOH), with turnover frequency values ranging between 6269 and 8093 h–1. Choosing the covalent complex Ir(MeBICAAC)Cl(COD)

  两亲性双环（烷基）（氨基）卡宾（ Me/iPr BICAAC）与[IrCl(COD)] 2反应后顺利生成单核Ir(I)配合物，并已对其进行了光谱和结构表征。这些配合物对使用异丙醇 (iPrOH) 的 4-氯苯甲醛转移氢化 (TH) 表现出良好的催化活性，周转频率值范围在 6269 至 8093 h –1之间。选择共价配合物 Ir( Me BICAAC)Cl(COD) 作为催化剂，对一系列用吸电子和给电子取代基功能化的羰基和亚胺进行了研究，并以中等到良好的产率提供了还原产物。当Ir( Me BICAAC)Cl(COD)在甲苯-d 8或异丙醇-d 8中长时间加热时，没有观察到BICAAC单元从Ir中心脱离，这证明了催化剂良好的热稳定性。配合物 Ir( Me BICAAC)Cl(COD) 还被发现对使用三乙基硅烷 (Et 3 SiH) 的多种醛的氢化硅烷化具有催化活性。