(5-chloro-2-methoxyphenyl)trimethylsilane | 708-49-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (5-chloro-2-methoxyphenyl)trimethylsilane
• 英文别名: 4-Chlor-2-trimethylsilyl-anisol；(5-chloro-2-methoxyphenyl)-trimethylsilane
• CAS: 708-49-6
• 化学式: C₁₀H₁₅ClOSi
• 分子量: 214.767
• InChiKey: RBGXDNQWKNRZFK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.89
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  乙醛酸乙酯 、 (5-chloro-2-methoxyphenyl)trimethylsilane 在 [Pd{(S)-BINAP}](SbF₆)2 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 48.0h， 生成
  参考文献：
  名称：

  乙醛酸酯与芳基硅烷的催化对映选择性丙烯酸化：光学活性扁桃酸衍生物的实用合成

  摘要：

  只是一点点的把戏！使用手性阳离子型钯配合物催化对映选择性芳基化提供了对映体富集的扁桃酸衍生物的可靠和有用的途径。这种实用方法的优点是催化剂负载量低（低至0.002 mol％）以及易于催化剂处理。

  DOI：

  10.1002/asia.201000522
• 作为产物：
  描述：

  4-氯苯甲醚 在 四氢呋喃 、 正丁基锂 作用下， 以 正己烷 、 环己烷 为溶剂， 反应 6.0h， 生成 (5-chloro-2-methoxyphenyl)trimethylsilane
  参考文献：
  名称：

  ortho-Lithiations Reassessed: the Advantages of Deficiency Catalysis in Hydrocarbon Media

  摘要：

  Hydrocarbon media based metalation procedures involving "deficiency catalysis" are described for the ortho-lithiation of anisole (A), p-chloroanisole (p-ClA), o-, m-, p-methylanisoles (o-, m-, p-MA), the three dimethoxybenzenes (DMB's), dimethylaniline (DMA), dimethybenzylamine (DMBA), m-methoxydimethylaniline (m-MeODM.A), and tetramethyl-p-phenylenediamine (p-TMPDA). These procedures involve certain mechanistic considerations, which must be fine-tuned to maximize the extent of metalation (EoM). Our working hypothesis is that a controlled deoligomerization of the n-BuLi hexamer found in hydrocarbon media will afford a "sweet spot" of deoligomerization such that a maximally efficient metalation medium can be formed. In many eases, a substoichiometric ratio of equivalent TMEDA to n-BuLi is 0.1-0.2:1.0, but certain substrates suffer multiple sites of metalation under these conditions, so different promoted hydrocarbon media systems incorporating measured equivalents of an ether have been formulated. This paper represents the summary of our successful efforts to render ortho-lithiations safer, greener, and more atom-economical by use of hydrocarbon solvent media. EoM's of 11 of the 12 substrates under these atom-economical conditions range from 87 to 97%.

  DOI：

  10.1021/om301120e

文献信息

• Ortho-metalation of p-chloroanisole: A media study
  作者：D.W Slocum、P Dietzel

  DOI：10.1016/s0040-4039(99)00161-6

  日期：1999.3

  As the chlorophenyl group is a pharmacophore, its stability toward metalation conditions in conjunction with the methoxy substituent was assessed. For p-chloroanisole metalation ortho to the methoxy group was achieved in high yield using increments of THF in cyclohexane; numerous other regimes afforded lower yields and a competing benzyne pathway. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.
• ortho-Lithiations Reassessed: the Advantages of Deficiency Catalysis in Hydrocarbon Media
  作者：D. W. Slocum、Thomas K. Reinscheld、Christopher B. White、Michael D. Timmons、Philip A. Shelton、Matthew G. Slocum、Rebecca D. Sandlin、Erica G. Holland、Damir Kusmic、John A. Jennings、Kristen C. Tekin、Quang Nguyen、Steven J. Bush、Julia M. Keller、Paul E. Whitley

  DOI：10.1021/om301120e

  日期：2013.3.25

  Hydrocarbon media based metalation procedures involving "deficiency catalysis" are described for the ortho-lithiation of anisole (A), p-chloroanisole (p-ClA), o-, m-, p-methylanisoles (o-, m-, p-MA), the three dimethoxybenzenes (DMB's), dimethylaniline (DMA), dimethybenzylamine (DMBA), m-methoxydimethylaniline (m-MeODM.A), and tetramethyl-p-phenylenediamine (p-TMPDA). These procedures involve certain mechanistic considerations, which must be fine-tuned to maximize the extent of metalation (EoM). Our working hypothesis is that a controlled deoligomerization of the n-BuLi hexamer found in hydrocarbon media will afford a "sweet spot" of deoligomerization such that a maximally efficient metalation medium can be formed. In many eases, a substoichiometric ratio of equivalent TMEDA to n-BuLi is 0.1-0.2:1.0, but certain substrates suffer multiple sites of metalation under these conditions, so different promoted hydrocarbon media systems incorporating measured equivalents of an ether have been formulated. This paper represents the summary of our successful efforts to render ortho-lithiations safer, greener, and more atom-economical by use of hydrocarbon solvent media. EoM's of 11 of the 12 substrates under these atom-economical conditions range from 87 to 97%.
• Catalytic Enantioselective Arylation of Glyoxylate with Arylsilanes: Practical Synthesis of Optically Active Mandelic Acid Derivatives
  作者：Kohsuke Aikawa、Yūta Hioki、Koichi Mikami

  DOI：10.1002/asia.201000522

  日期：2010.11.2

  a little does the trick! The catalytic enantioselective arylation using chiral dicationic palladium complexes provides a reliable and useful access to enantiomerically enriched mandelic‐acid derivatives. Significantly low catalyst loading (down to 0.002 mol %) as well as easy catalyst handling are the advantage of this practical method.

  只是一点点的把戏！使用手性阳离子型钯配合物催化对映选择性芳基化提供了对映体富集的扁桃酸衍生物的可靠和有用的途径。这种实用方法的优点是催化剂负载量低（低至0.002 mol％）以及易于催化剂处理。