Bis-benzhydryloxy-diphenyl-silane | 66774-56-9

• 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: Bis-benzhydryloxy-diphenyl-silane
• 英文别名: Dibenzhydryloxy(diphenyl)silane
• CAS: 66774-56-9
• 化学式: C₃₈H₃₂O₂Si
• 分子量: 548.756
• InChiKey: FZYUNRCOXRXQTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.86
• 重原子数：
  41
• 可旋转键数：
  10
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (benzhydryloxy)diphenylsilane 在 C₂₆H₄₃Cu₂N₂P₂^(1-)*C₁₂H₂₄KO₆⁽¹⁺⁾ 作用下， 以 四氢呋喃 为溶剂， 反应 3.33h， 生成 Bis-benzhydryloxy-diphenyl-silane
  参考文献：
  名称：

  一种结构明确的阴离子一氢化二铜 (I) 络合物，其反应类似于簇**

  摘要：

  据报道，一种罕见的、结构明确的氢化二铜 (Cu 2 H) 络合物，其表现出与已知 Cu 2 Hs 不同的反应性。使用实验和计算相结合的方法，我们将簇状反应性归因于扩张的钳配体的刚性双核性质，这阻止了溶液中单核 CuH 的形成。

  DOI：

  10.1002/anie.202202318

文献信息

• Hydrosilylation of Ketones Catalyzed by Iron Iminobipyridine Complexes and Accelerated by Lewis Bases
  作者：Katsuaki Kobayashi、Yosuke Izumori、Daisuke Taguchi、Hiroshi Nakazawa

  DOI：10.1002/cplu.201900366

  日期：2019.8

  in the hydrosilylation of ketones appeared to be the reductive elimination of alkoxy and silyl groups from the iron center, which was facilitated by the coordination of N-donor ligand to the iron. This coordination ability of the N-donor ligand, however, inhibited olefin hydrosilylation. Addition of KOt Bu instead of N-donor also showed the same acceleration and inhibition effects on ketone and olefin

  发现Fe-亚氨基联吡啶络合物（（R BPIAr，R′）FeBr 2，R BPIAr，R′＝亚氨基联吡啶衍生物）表现出对酮的氢化硅烷化的良好催化活性。对于2-辛酮与苯基硅烷的硅氢加成反应，可获得最高的TOF（周转频率）。各种4-取代的苯乙酮衍生物的反应表明，在4-位引入吸电子基团阻碍了反应。4-氯苯乙酮与二苯甲硅烷的硅氢加成反应的TOF值很低（30 min-1），但是催化量的路易斯碱（尤其是吡啶）的加入显着加速了这种硅氢加成反应（980 min-1）。比较几种N-供体配体的累加效应表明，N-供体配体的配位能力是加速的原因。酮氢化硅烷化的速率决定步骤似乎是从铁中心还原性消除烷氧基和甲硅烷基，这是由于N供体配体与铁的配位作用而促进的。然而，N-给体配体的这种配位能力抑制了烯烃的氢化硅烷化。加入KOt Bu代替N-给体也分别显示出相同的促进和抑制作用，分别对酮和烯烃进行了氢甲硅烷基化。然而，N-给
• Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation
  作者：Ramkumar Kannan、Selvakumar Balasubramaniam、Sandeep Kumar、Raju Chambenahalli、Eluvathingal D. Jemmis、Ajay Venugopal

  DOI：10.1002/chem.202002006

  日期：2020.10.6

  [(Me2NC6H4)Bi(L)3]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single‐crystal X‐ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si−H addition.

  铋化合物作为过渡金属配合物和电子贫乏的轻质p嵌段化合物在均相催化中的潜在替代品正变得越来越重要。通过分离[Me 2 NC 6 H 4 } Bi OP（NMe 2）3 } 3，实验证明了具有三个亲电位点的双坐标[（Me 2 NC 6 H 4）Bi] 2+的计算分析。] [B（3,5-C 6 H 3 Cl 2）4 ] 2。这些观察结果使我们产生了有机二有机铋催化剂，[（Me 2NC 6 H 4）Bi（L）3 ] 2+（L =醛/酮），通过溶液中的NMR光谱和固态的单晶X射线衍射证明。它有效地催化醛和酮的氢化硅烷化反应，从而使甲硅烷基醚成为唯一的高收率产品。我们的研究支持铋中心的羰基活化机理，然后再加入Si-H。
• A Remarkably Active Iron Catecholate Catalyst Immobilized in a Porous Organic Polymer
  作者：Steven J. Kraft、Raúl Hernández Sánchez、Adam S. Hock

  DOI：10.1021/cs400043a

  日期：2013.5.3

  single-site, iron catecholate-containing porous organic polymer was prepared and utilized as a stable and remarkably active catalyst for the hydrosilylation of ketones and aldehydes. In some instances, catalyst loadings of 0.043–2.1 mol % [Fe] were sufficient for complete hydrosilylation of aldehydes and ketones within 15 min at room temperature. The catalyst can be recycled at least three times without

  制备了单部位的含儿茶酚酸铁的多孔有机聚合物，并将其用作稳定和显着活性的催化剂，用于酮和醛的氢化硅烷化。在某些情况下，0.043–2.1 mol％[Fe]的催化剂负载量足以在室温下15分钟内将醛和酮完全氢化硅烷化。催化剂可以循环至少三次而不会降低催化活性。该系统是没有均相类似物的固定化均相催化剂的一个实例。
• Robust Two-Coordinate Zn(II) Organocations Supported by Bulky-Yet-Flexible IPr* Carbene: Synthesis, Structure, and Distinct Reactivity in Hydrosilylation Catalysis
  作者：Xuejuan Xu、Christophe Gourlaouen、Béatrice Jacques、Samuel Dagorne

  DOI：10.1021/acs.organomet.3c00282

  日期：2023.10.9

  [IPr*-ZnR]+ series are less Lewis acidic than their [IPr-ZnR]+, yet they display a distinct reactivity in hydrosilylation catalysis. Thus, cation [6]+ catalyzes at room-temperature styrene and alkyne hydrosilylation with HSiEt3 as the silane source. Remarkably, it is also a highly effective ketone/aldehyde hydrosilylation catalysis for a rather broad silane and ketone scope and performs much better than

  本研究详细介绍了 [IPr*-Zn-R] + (IPr* = 1,3-双[2,6-双(二苯基甲基)-4-]类型的新型 Zn(II) 基有机阳离子的合成和表征[甲基苯基]-1,3-二氢-2H-咪唑-2-亚基；R=烷基、芳基）及其在苯乙烯、炔烃和羰基硅氢加成催化中的应用。通过IPr*与等摩尔量的ZnR 2反应制备中性IPr*加合物[IPr*-ZnR 2 ] ( 1 , R = Me; 2 , R = Et; 3 , R = Ph)并在良好的条件下分离。产量。尽管 IPr* 存在严重的空间位阻，但化合物1 – 3在溶液中具有鲁棒性，反映了卡宾 IPr* 体积大但灵活的性质。加合物1和2可以很容易地被 [Ph 3 C][B(C 6 F 5 ) 4 ] 电离，产生双配位 Zn(II) 阳离子 [IPr*-ZnMe] + ([ 4 ] + ) 和 [IPr *-ZnEt] + ([ 5 ] + )，两者均以
• Hydrosilylation of Aldehydes and Ketones Catalyzed by a Terminal Zinc Hydride Complex, [κ³-Tptm]ZnH
  作者：Wesley Sattler、Serge Ruccolo、Mahnaz Rostami Chaijan、Tawfiq Nasr Allah、Gerard Parkin

  DOI：10.1021/acs.organomet.5b00506

  日期：2015.10.12

  Tris(2-pyridylthio)methyl zinc hydride, [kappa(3)-Tptm]ZnH, is an effective catalyst for multiple insertions of carbonyl groups into the Si-H bonds of PhxSiH4-x (x = 1, 2). Specifically, [kappa(3)-Tptm]ZnH catalyzes the insertion of a variety of aldehydes and ketones into the Si-H bonds of PhSiH3 and Ph2SiH2 to afford PhSi[OCH(R)R'](3) and Ph,Si[OCH(R)R'](2), respectively. The mechanism for hydrosilylation is proposed to involve insertion of the carbonyl group into the Zn-H bond to afford an alkoxy species, followed by metathesis with the silane to release the alkoxysilane and regenerate the zinc hydride catalyst. Multiple insertion of prochiral ketones results in the formation of diastereomeric mixtures of alkoxysilanes that can be identified by NMR spectroscopy.