(2-methoxyphenyl)dimethyl(phenyl)silane

• 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)dimethyl(phenyl)silane
• 英文别名: (2-Methoxyphenyl)-dimethyl-phenylsilane；(2-methoxyphenyl)-dimethyl-phenylsilane
• 化学式: C₁₅H₁₈OSi
• 分子量: 242.393
• InChiKey: GYUJNKGXZJSOSX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.52
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 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)dimethyl(phenyl)silane 、 tert-butyldiphenyl(phenylselanyl)silane 在 9,10-二甲氧基蒽 作用下， 以 乙腈 为溶剂， 反应 18.0h， 以62%的产率得到tert-butyl(4-methoxyphenyl)diphenylsilane
  参考文献：
  名称：

  通过有机光氧化还原催化对芳烃进行 p-甲硅烷基化：使用 p-甲硅烷基化芳烃进行专有的 o-甲硅烷基化、o-酰化和 o-烷基化反应

  摘要：

  通过将原位生成的甲硅烷基自由基与芳烃自由基阳离子偶联，已经实现了芳烃的光催化区域特异性p-甲硅烷基化。该策略包括 PhSe-SiR 3 的还原活化和从富电子芳烃到 9,10-二甲氧基蒽自由基阳离子 (DMA •+ ) 的单电子转移。如此形成的对-甲硅烷基芳烃进一步用于排他性的o-甲硅烷基化反应和区域特异性的o-酰化以及o-烷基化反应。

  DOI：

  10.1021/acs.orglett.1c02672
• 作为产物：
  描述：

  2-(2-甲氧基苯基)-1,3-二噻烷 在 bis(1,5-cyclooctadiene)nickel (0) 、 正丁基锂 、 iron(III)-acetylacetonate 、 三丁基膦 、 双氧水 、 sodium iodide 、 锌 作用下， 以 四氢呋喃 、 正己烷 、 水 、 乙酸乙酯 、 甲苯 为溶剂， 反应 38.0h， 生成 (2-methoxyphenyl)dimethyl(phenyl)silane
  参考文献：
  名称：

  镍催化的甲硅烷基酮合成硅烷。

  摘要：

  描述了一种空前的镍催化脱羰基甲硅烷化反应，该反应是通过CO挤出的非应变和非定向基团辅助的甲硅烷基酮的分子内重组片段偶联而实现的。这种廉价且容易获得的催化剂可在温和的反应条件下发挥作用，并能够合成结构多样的芳基硅烷，包括杂环和天然产物衍生物。

  DOI：

  10.1021/acs.orglett.9b03487

文献信息

• Activator-Free Palladium-Catalyzed Silylation of Aryl Chlorides with Silylsilatranes
  作者：Yutaro Yamamoto、Hiroshi Matsubara、Kei Murakami、Hideki Yorimitsu、Atsuhiro Osuka

  DOI：10.1002/asia.201402595

  日期：2015.1

  The palladium‐catalyzed silylation of aryl chlorides with silylsilatranes proceeds under activator‐free conditions; hence, wide functional group compatibility is displayed and boryl and siloxy groups are able to survive. Experimental and computational studies revealed that smooth transmetalation from the silylsilatrane to the arylpalladium chloride is facilitated by strong interaction between the Lewis

  在无活化剂的条件下，钯催化的芳基氯与甲硅烷基硅烷基化的甲硅烷基化反应得以进行。因此，显示出广泛的官能团相容性，并且硼烷基和甲硅烷氧基能够存活。实验和计算研究表明，路易斯酸性硅与氯化物之间的强相互作用促进了从甲硅烷基硅石到芳基钯氯化物的平滑过渡金属化。
• Nickel‐Catalyzed Reaction of Aryl 2‐Pyridyl Ethers with Silylzinc Chlorides: Silylation of Aryl 2‐Pyridyl Ethers via Cleavage of the Carbon−Oxygen Bond
  作者：Ying‐Ying Kong、Zhong‐Xia Wang

  DOI：10.1002/adsc.201900949

  日期：2019.12.3

  Ni‐catalyzed C−O(Py) bond activation and silylation of aryl 2‐pyridyl ethers with silylzinc chlorides were carried out. This protocol allowed the 2‐pyridyloxy group to be substituted by a silyl group with short reaction times, mild reaction conditions, and good compatibility of functional groups.

  进行了Ni催化的C-O（Py）键活化和芳基2-吡啶基醚与甲硅烷基氯化锌的甲硅烷基化反应。该方案允许2-吡啶氧基被甲硅烷基取代，反应时间短，反应条件温和且官能团相容性好。
• Mechanochemical Synthesis of Arylsilanes via Barbier‐Type Reaction between Aryl Halides and Chlorosilanes with Magnesium
  作者：Lianze Zong、Ruizhi Sun、Xixi Hu、Jiarui Zhang、Yanbin Luan、Zhengbao. Xu、Caixia Xie、Xinjin Li、Feng‐Gang Sun、Hui Liu、Zhong‐Quan Liu、Zengdian Zhao、Lizhi Zhang

  DOI：10.1002/adsc.202301244

  日期：2024.4.9

  The reaction of chlorosilanes with organometallic reagents is an old and well‐developed approach to organosilicon compounds, however, its application was limited due to the sensitivity of organometallic reagents to air, water. Here we display a mechanochemical access to arylsilanes via Barbier‐type reaction of chlorosilanes with aryl halide with magnesium. By treatment of the two halides with Mg powder under electromagnetic milling, a series of arylsilanes are obtained within 15 minutes. Taking the advantages of the electromagnetic milling, this protocol features transition‐metal free, good functional group tolerance, air stable and mild conditions.

  摘要氯硅烷与有机金属试剂的反应是一种古老而成熟的有机硅化合物制备方法，但由于有机金属试剂对空气和水的敏感性，其应用受到限制。在这里，我们展示了一种通过氯硅烷与芳基卤化物和镁的巴比耶型反应来获得芳基硅烷的机械化学方法。在电磁研磨条件下用镁粉处理这两种卤化物，15 分钟内就能得到一系列芳基硅烷。利用电磁研磨的优势，该方案具有无过渡金属、官能团耐受性好、空气稳定和条件温和等特点。
• Direct and Selective Arylation of Tertiary Silanes with Rhodium Catalyst
  作者：Yoshinori Yamanoi、Hiroshi Nishihara

  DOI：10.1021/jo8008148

  日期：2008.9.1

  We have developed a convenient and efficient approach to the arylation of tertiary silanes under mild conditions. A variety of arylsilanes were synthesized in a one-step process with good to excellent yields in the presence of a rhodium catalyst with a base. The reaction was highly solvent dependent, and amides were the most effective of the various solvents used. This common catalyst system is highly tolerant of the various sensitive functional groups on the substrates, which might be difficult to extract by other methods. The rhodium-promoted silylation of aryl halides with electron-donating groups occurred more efficiently than the silylation of aryl halides substituted with electron-withdrawing groups. Heteroaromatic halides were also found to be readily silylated with tertiary silanes. The successful application of this reaction to the synthesis of a TAC-101 analogue, which is a trialkylsilyl-containing synthetic retinoid benzoic acid derivative with selective binding affinity for retinoic acid receptor-alpha, is also described.
• Rhodium-catalyzed silylation of ortho-functionalized aryl halides with hydrosilanes
  作者：Yoshinori Yamanoi、Hiroshi Nishihara

  DOI：10.1016/j.tetlet.2006.08.001

  日期：2006.10

  The silylation of ortho-functionalized aryl iodide with trialkylsilanes in the presence of RhCl(CO)(PPh3)(2) or [Rh(cod)(2)]BF4 and K3PO4 provides the corresponding arylalkylsilane in good to high yield. This catalytic system showed a dramatically different activity when Pd(t-Bu3P)(2) was used as a catalyst. (c) 2006 Elsevier Ltd. All rights reserved.