1-(4-Chlorophenyl)ethoxy-diethylsilane | 1257334-03-4

• 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: 1-(4-Chlorophenyl)ethoxy-diethylsilane
• CAS: 1257334-03-4
• 化学式: C₁₂H₁₉ClOSi
• 分子量: 242.821
• InChiKey: GWOKNEHPHKBGNO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.18
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  1-(4-Chlorophenyl)ethoxy-diethylsilane 在 di-μ-chlorobis(norbornadiene)dirhodium(I) 、 norbornene 、 三(4-甲氧苯基)膦 作用下， 以 四氢呋喃 为溶剂， 以156.1 mg的产率得到6-chloro-1,1-diethyl-3-methyl-1,3-dihydrobenzo[c][1,2]oxasilole
  参考文献：
  名称：

  模块化的方法来还原ç SP2 -H和C SP3 -H通过单锅，连续过渡金属催化羧酸衍生物的硅烷化

  摘要：

  我们报告了一种模块化方法，用于催化还原性C sp2- H和C sp3- H甲酸酯基，包括酯，酮和醛的羧酸衍生物的甲硅烷基化。Ir（I）/ Rh（I）或Rh（I）/ Rh（I）序列的选择分别导致详尽的还原性酯或还原性酮/醛甲硅烷基化。值得注意的是，提出了一种催化剂控制的直接还原的双还原甲硅烷基醚的形成方法，特别是通过Ir催化的详尽的氢化硅烷化反应。生成的甲硅烷基醚在单个容器中进行C sp2- H和苄基C sp3- H甲硅烷基化。

  DOI：

  10.1021/acs.joc.5b00564
• 作为产物：
  描述：

  二乙基硅烷 、 对氯苯乙酮 在 di-μ-chlorobis(norbornadiene)dirhodium(I) 、 三(4-甲氧苯基)膦 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 生成 1-(4-Chlorophenyl)ethoxy-diethylsilane
  参考文献：
  名称：

  模块化的方法来还原ç SP2 -H和C SP3 -H通过单锅，连续过渡金属催化羧酸衍生物的硅烷化

  摘要：

  我们报告了一种模块化方法，用于催化还原性C sp2- H和C sp3- H甲酸酯基，包括酯，酮和醛的羧酸衍生物的甲硅烷基化。Ir（I）/ Rh（I）或Rh（I）/ Rh（I）序列的选择分别导致详尽的还原性酯或还原性酮/醛甲硅烷基化。值得注意的是，提出了一种催化剂控制的直接还原的双还原甲硅烷基醚的形成方法，特别是通过Ir催化的详尽的氢化硅烷化反应。生成的甲硅烷基醚在单个容器中进行C sp2- H和苄基C sp3- H甲硅烷基化。

  DOI：

  10.1021/acs.joc.5b00564

文献信息

• Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
  申请人：The University of Chicago

  公开号：US10647733B2

  公开（公告）日：2020-05-12

  Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

  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。
• 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。
• Bipyridine- and Phenanthroline-Based Metal–Organic Frameworks for Highly Efficient and Tandem Catalytic Organic Transformations via Directed C–H Activation
  作者：Kuntal Manna、Teng Zhang、Francis X. Greene、Wenbin Lin

  DOI：10.1021/ja512478y

  日期：2015.2.25

  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.
• 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.