Diethyl-[1-(4-methylphenyl)ethoxy]silane | 1601301-33-0

• 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: Diethyl-[1-(4-methylphenyl)ethoxy]silane
• CAS: 1601301-33-0
• 化学式: C₁₃H₂₂OSi
• 分子量: 222.403
• InChiKey: MSWAGLJQIVFURG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Diethyl-[1-(4-methylphenyl)ethoxy]silane 在 6C₁₂H₆N₂O₄^(2-)*6Zr⁽⁴⁺⁾*4HO^(1-)*4O^(2-)*6Ir⁽¹⁺⁾*6CH₃O^(1-)*6C₈H₁₂ 作用下， 以 正庚烷 为溶剂， 反应 30.0h， 以92%的产率得到1,1-diethyl-3,6-dimethyl-3H-2,1-benzoxasilole
  参考文献：
  名称：

  Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations

  摘要：

  基于以氮为供体的有机桥联配体，包括基于1,3-二酮亚胺（NacNac）、联吡啶和柳酸亚胺的金属-有机框架（MOFs）组成物被合成，然后用金属前驱体如第一行过渡金属的络合物进行后合成金属化。有机桥联配体的金属络合物也可以直接并入MOFs中。MOFs提供了一个多功能的、可回收和可重复使用的单点固体催化剂家族，用于催化各种不对称有机转化。这些固体催化剂也可以集成到流动反应器或超临界流体反应器中。

  公开号：

  US10647733B2
• 作为产物：
  描述：

  二乙基硅烷 、 对甲基苯乙酮 在 6Zr⁽⁴⁺⁾*4O^(2-)*4HO^(1-)*4C₁₈H₁₂O₄^(2-)*2C₁₆H₁₀N₂O₄^(2-)*C₈H₁₂*Ir⁽¹⁺⁾*CH₃O^(1-) 作用下， 以 正庚烷 为溶剂， 反应 18.0h， 生成 Diethyl-[1-(4-methylphenyl)ethoxy]silane
  参考文献：
  名称：

  Bipyridine- and Phenanthroline-Based Metal–Organic Frameworks for Highly Efficient and Tandem Catalytic Organic Transformations via Directed C–H Activation

  摘要：

  We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal-organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C-H borylation of arenes using B2pin2. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C-H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.

  DOI：

  10.1021/ja512478y

文献信息

• Ruthenium-Catalyzed Dehydrogenative Intermolecular O-H/Si-H/C-H Silylation: Synthesis of (E)-Alkenyl Silyl-Ether and Silyl-Ether Heterocycle
  作者：Ziwei Huang、Qiao Lin、Jiefang Li、Shanshan Xu、Shaohuan Lv、Feng Xie、Jun Wang、Bin Li

  DOI：10.3390/molecules28207186

  日期：——

  Selective dehydrogenative silylation is one of the most valuable tools for synthesizing organosilicon compounds. In this study, a regio- and stereoselective ruthenium-catalyzed dehydrogenative intermolecular silylation was firstly developed to access (E)-alkenyl silyl-ether derivatives and silyl-ether heterocycles with good functional group tolerance. Furthermore, two pathways for RuH2(CO)(PPh3)3/NBE-catalyzed

  选择性脱氢硅烷化是合成有机硅化合物最有价值的工具之一。在这项研究中，首先开发了一种区域和立体选择性钌催化的脱氢分子间硅烷化反应，以获得具有良好官能团耐受性的(E)-烯基甲硅烷基醚衍生物和甲硅烷基醚杂环。此外，以H2SiEt2为氢硅烷试剂，研究了RuH2(CO)(PPh3)3/NBE催化的醇和烯烃的脱氢分子间硅烷化以及萘酚衍生物的分子间硅烷化的两种途径。
• Postsynthetic Metalation of Bipyridyl-Containing Metal–Organic Frameworks for Highly Efficient Catalytic Organic Transformations
  作者：Kuntal Manna、Teng Zhang、Wenbin Lin

  DOI：10.1021/ja5018267

  日期：2014.5.7

  We have designed highly stable and recyclable single-site solid catalysts via postsynthetic metalation of the 2,2'-bipyridyl-derived metal organic framework (MOF) of the UiO structure (bpy-UiO). The Ir-functionalized MOF (bpy-UiO-Ir) is a highly active catalyst for both borylation of aromatic C-H bonds using B-2(pin)(2) (pin = pinacolate) and ortho-silylation of benzylicsilyl ethers; the ortho-silylation activity of the bpy-UiO-Ir is at least 3 orders of magnitude higher than that of the homogeneous control. The Pd-functionalized MOF (bpy-UiO-Pd) catalyzes the dehydrogenation of substituted cyclohexenones to afford phenol derivatives with oxygen as the oxidant. Most impressively, the bpy-UiO-Ir was recycled and reused 20 times for the borylation reaction without loss of catalytic activity or MOF crystallinity. This work highlights the opportunity in designing highly stable and active catalysts based on MOFs containing nitrogen donor ligands for important organic transformations.