(2-methoxyphenyl)silane | 380442-64-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (2-methoxyphenyl)silane
• 英文别名: (2-Methoxyphenyl)silane
• CAS: 380442-64-8
• 化学式: C₇H₁₀OSi
• 分子量: 138.241
• InChiKey: TWUKNTFPPQAXCC-UHFFFAOYSA-N

物化性质

• 沸点：
  184.4±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.31
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  (2-methoxyphenyl)silane 在 C₃₀H₅₄CaN₄Si 作用下， 以 氘代苯 为溶剂， 反应 2.0h， 以99%的产率得到Tri-(o-methoxyphenyl)-silan
  参考文献：
  名称：

  有机钙络合物催化的 ArSiH 3或 Ar(烷基)SiH 2选择性再分布到 Ar 3 SiH 或 Ar 2 (烷基)SiH

  摘要：

  钙是一种丰富的、生物相容的、环境友好的元素。有机钙配合物在有机合成中用作催化剂最近取得了一些突破，但报道的反应类型仍然有限。另一方面，氢硅烷是有机和聚合物合成中非常重要的试剂，通过 C-Si 和 Si-H 键断裂和重整对氢硅烷的重新分布提供了使此类化合物的范围多样化的直接策略。在此，我们报告了由基于 β-二酮亚胺基的四齿配体支持的两种烷基钙配合物的合成和结构表征。这两种烷基钙配合物与 PhSiH 3反应生成氢化钙配合物，氢化配合物的稳定性取决于支持配体。一种钙烷基复杂有效地催化ArSiH的选择性再分配3或Ar（烷基）的SiH 2与Ar 3的SiH和SiH 4或Ar 2（烷基）的SiH和alkylSiH 3分别。更重要的是，这种烷基钙配合物还催化了吸电子取代的Ar(R)SiH 2和供电子取代的Ar'(R)SiH 2之间的交叉偶联，以良好的产率生产ArAr'（烷基）SiH。合成的ArAr'（烷基）SiH

  DOI：

  10.1021/acscatal.1c00463
• 作为产物：
  描述：

  2-溴苯甲醚 在 正丁基锂 、 四氯化硅 、 lithium aluminium tetrahydride 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 2.0h， 以68%的产率得到(2-methoxyphenyl)silane
  参考文献：
  名称：

  Mechanistic Aspects of Samarium-Mediated σ-Bond Activations of Arene C−H and Arylsilane Si−C Bonds

  摘要：

  To investigate the potential role of Sm-Ph species as intermediates in the samarium-catalyzed redistribution of PhSiH3 to Ph2SiH2 and SiH4, the samariurn phenyl complex [Cp*2SmPh](2) (1) was prepared by oxidation of Cp*Sm-2 (2) with HgPh2. Compound 1 thermally decomposes to yield benzene and the phenylene-bridged disamarium complex CP*Sm-2(mu -1,4-C6H4)SmCp*(2) (3). This decomposition reaction appears to proceed through dissociation of 1 into monomeric CP*2SmPh species which then react via unimolecular and bimolecular pathways, involving rate-limiting Cp* metalation and direct C-H activation, respectively. The observed rate law for this process is of the form: rate = k(1)[1] + k(2)[1](2) Complex I efficiently transfers its phenyl. group to PhSiH3, with formation of Ph2SiH2 and [Cp*Sm-2(mu -H)](2) (4). Quantitative Si-C bond cleavage Of C6F5SiH3 is effected by the samarium hydride complex 4, yielding silane and [Cp*Sm-2(mu -C6F5)](2) (5). In contrast, Si-H activation takes place upon reaction of 4 with o-MeOC6H4SiH3, affording the samarium. silyl species Cp*2SmSiH2(o-MeOC6H4) (7). Complex 7 rapidly decomposes to [Cp*Sm-2(mu -0-MeOC6H4)](2) (6) and other samarium-containing products. Compounds 5 and 6 were prepared independently by oxidation of 2 with Hg(C6F5)(2), and Hg(o-MeOC6H4)(2), respectively. The mechanism of samarium-mediated redistribution at silicon, and chemoselectivity in sigma -bond metathesis reactions, are discussed.

  DOI：

  10.1021/ja011472w

文献信息

• Radiochemical and Quantum-Chemical Study of the Migration of the Cationic Center in the SiC6H+7 Ion
  作者：E. A. Shishigin、V. V. Avrorin、T. A. Kochina、I. S. Ignat'ev、E. N. Sinotova

  DOI：10.1007/s11176-005-0435-3

  日期：2005.9

  The reactions of silylphenyl and phenylsilyl cations with methyl tert-butyl ether were studied radiochemically. The phenylsilylium ion is more stable thermodynamically than its isomers with the charge localized on carbon atoms of the benzene ring. Because of the high activation barriers to migration of the cationic center over the benzene ring (according to B3LYP/6-31G* calculations), only the ortho isomer can transform into the silylium ion.

  对硅苯基和苯硅基阳离子与叔丁基甲醚的反应进行了放射化学研究。苯硅阳离子在热力学上比其同分异构体（带电荷集中在苯环碳原子上的异构体）更稳定。由于阳离子中心在苯环上迁移的激活能障碍较高（根据B3LYP/6-31G*计算），只有邻位异构体能够转化为硅阳离子。
• Cobalt-Catalyzed Diastereoselective and Enantioselective Hydrosilylation of Achiral Cyclopropenes
  作者：Longyang Dian、Ilan Marek

  DOI：10.1021/acs.orglett.0c01833

  日期：2020.6.19

  A mild diastereoselective and enantioselective cobalt-catalyzed hydrosilylation reaction of achiral cyclopropenes has been developed. In this protocol, various substituted cyclopropenes and arylsilanes were transformed, in the presence of readily available chiral cobalt complex, into silylcyclopropanes with high selectivities.

  已经开发了温和的非对映选择性和对映选择性的钴催化的非手性环丙烯的氢化硅烷化反应。在该方案中，在容易获得的手性钴配合物的存在下，将各种取代的环丙烯和芳基硅烷转化为具有高选择性的甲硅烷基环丙烷。
• Stabilization of ArSiH₄⁻and SiH₆²⁻Anions in Diruthenium SiH σ-Complexes
  作者：Mark C. Lipke、T. Don Tilley

  DOI：10.1002/anie.201202328

  日期：2012.10.29

  Hydridosilicate anions ([ArSiH4]− and [SiH6]2−) were stabilized as ligands in diruthenium SiH σ‐complexes [(PhBPPh3)Ru}2(μ‐Cl)(μ‐η3,η3‐H4SiAr)] (Ar=2‐MeOC6H4, Mes, Ph) and [(PhBPPh3)Ru}2(μ‐η4,η4‐H6Si)] (see picture). These complexes were formed under mild conditions and characterized by single‐crystal X‐ray diffraction (see picture), NMR and IR spectroscopy, and computational techniques.

  Hydridosilicate阴离子（[ArSiH 4 ] -和[的SiH 6 ] 2-）的稳定化在二钌的Si配体 ħσ络合物[（PhBP博士3）的Ru} 2（μ-Cl）的（μ-η 3，η 3 -H 4 SIAR）]（Ar为2- MeOC 6 ħ 4，MES，PH）和[（PhBP博士3）的Ru} 2（μ-η 4，η 4 -H 6Si）]（见图）。这些络合物是在温和条件下形成的，并通过单晶X射线衍射（见图），NMR和IR光谱以及计算技术来表征。
• Copper-Catalyzed Highly Selective Hydrosilylation of Silyl or Boryl Alkene: A Method for Preparing Chiral Geminated Disilyl and Borylsilyl Reagents
  作者：Min Zhang、Yuqi Ji、Zheng Zhang、Chun Zhang

  DOI：10.1021/acs.orglett.2c00858

  日期：2022.4.15

  The copper-catalyzed highly selective hydrosilylation of silyl or boryl alkene has been developed. This chemistry could afford a practical method for preparing chiral geminated disilyl and borylsilyl reagents, which are useful organosilanes and versatile synthons for organic synthesis. The experimental data suggested that this reaction could be compatible with a variety of functional groups. Furthermore

  已经开发了铜催化的甲硅烷基或硼基烯烃的高选择性氢化硅烷化。这种化学方法可以提供一种实用的方法来制备手性双甲硅烷基和硼基甲硅烷基试剂，它们是有用的有机硅烷和用于有机合成的多功能合成子。实验数据表明该反应可以与多种官能团相容。此外，可以通过这种化学方法制备的偕二金属化合物的实用性已通过进一步的转化得到很好的说明。
• Enantioselective synthesis of acyclic monohydrosilanes by steric hindrance assisted C–H silylation
  作者：Delong Mu、Shuqiong Pan、Xiaoyu Wang、Xiaoyun Liao、Yong Huang、Jiean Chen

  DOI：10.1039/d2cc02307e

  日期：——

  Herein, a rhodium-catalyzed desymmetrization of dihydrosilanes with heterocyclic compounds via intermolecular dehydrogenative C–H silylation is developed.

  在此，开发了一种通过铑催化的二氢硅烷与杂环化合物的不对称化反应，通过分子间脱氢C-H硅化反应实现。