1-sec-butoxy-3,5-dimethylbenzene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-sec-butoxy-3,5-dimethylbenzene
• 英文别名: 1-Butan-2-yloxy-3,5-dimethylbenzene
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: HSQGJIQYTVRUOI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  13
• 可旋转键数：
  3
• 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-sec-butoxy-3,5-dimethylbenzene 在 (^iPr4PCOP)Ir(C2H4) 作用下， 以 对二甲苯 为溶剂， 200.0 ℃ 、1.33 Pa 条件下， 反应 16.0h， 生成 3,5-二甲基苯酚
  参考文献：
  名称：

  醚的C催化切割？夹钳铱配合物的O键

  摘要：

  发展有效的催化方法以裂解醚的相对不活泼的CO键仍然是催化方面的重要挑战。在我们小组最近的工作的基础上，我们报告了使用夹钳铱催化剂进行的芳基烷基醚的脱氢芳氧基化反应。该方法代表了罕见的完全经济的醚CO键裂解方法。

  DOI：

  10.1002/anie.201402576
• 作为产物：
  描述：

  丁烯 、 3,5-二甲基苯酚 在 C₁₉H₃₇IrOP₂ 作用下， 以 对二甲苯 为溶剂， 150.0 ℃ 、202.66 kPa 条件下， 反应 96.0h， 生成 1-sec-butoxy-3,5-dimethylbenzene
  参考文献：
  名称：

  Olefin Hydroaryloxylation Catalyzed by Pincer–Iridium Complexes

  摘要：

  Aryl alkyl ethers, which are widely used throughout the chemical industry, are typically produced via the Williamson ether synthesis. Olefin hydroaryloxylation potentially offers a much more atom-economical alternative. Known acidic catalysts for hydroaryloxylation, however, afford very poor selectivity. We report the organometallic-catalyzed intermolecular hydroaryloxylation of unactivated olefins by iridium "pincer" complexes. These catalysts do not operate via the hidden Bronsted acid pathway common to previously developed transition-metal-based catalysts. The reaction is proposed to proceed via olefin insertion into an iridium-alkoxide bond, followed by rate-determining C-H reductive elimination to yield the ether product. The reaction is highly chemo- and regioselective and offers a new approach to the atom-economical synthesis of industrially important ethers and, potentially, a wide range of other oxygenates.

  DOI：

  10.1021/ja404566v

文献信息

• Catalytic Cleavage of Ether CO Bonds by Pincer Iridium Complexes
  作者：Michael C. Haibach、Nicholas Lease、Alan S. Goldman

  DOI：10.1002/anie.201402576

  日期：2014.9.15

  The development of efficient catalytic methods to cleave the relatively unreactive CO bonds of ethers remains an important challenge in catalysis. Building on our group’s recent work, we report the dehydroaryloxylation of aryl alkyl ethers using pincer iridium catalysts. This method represents a rare fully atom‐economical method for ether CO bond cleavage.

  发展有效的催化方法以裂解醚的相对不活泼的CO键仍然是催化方面的重要挑战。在我们小组最近的工作的基础上，我们报告了使用夹钳铱催化剂进行的芳基烷基醚的脱氢芳氧基化反应。该方法代表了罕见的完全经济的醚CO键裂解方法。
• Olefin Hydroaryloxylation Catalyzed by Pincer–Iridium Complexes
  作者：Michael C. Haibach、Changjian Guan、David Y. Wang、Bo Li、Nicholas Lease、Andrew M. Steffens、Karsten Krogh-Jespersen、Alan S. Goldman

  DOI：10.1021/ja404566v

  日期：2013.10.9

  Aryl alkyl ethers, which are widely used throughout the chemical industry, are typically produced via the Williamson ether synthesis. Olefin hydroaryloxylation potentially offers a much more atom-economical alternative. Known acidic catalysts for hydroaryloxylation, however, afford very poor selectivity. We report the organometallic-catalyzed intermolecular hydroaryloxylation of unactivated olefins by iridium "pincer" complexes. These catalysts do not operate via the hidden Bronsted acid pathway common to previously developed transition-metal-based catalysts. The reaction is proposed to proceed via olefin insertion into an iridium-alkoxide bond, followed by rate-determining C-H reductive elimination to yield the ether product. The reaction is highly chemo- and regioselective and offers a new approach to the atom-economical synthesis of industrially important ethers and, potentially, a wide range of other oxygenates.