5-methoxy-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indole | 1219637-79-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 5-methoxy-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indole
• 英文别名: 5-methoxy-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole
• CAS: 1219637-79-2
• 化学式: C₁₅H₂₀BNO₃
• 分子量: 273.14
• InChiKey: HXDLIEHKTHDXQH-UHFFFAOYSA-N

物化性质

• 密度：
  1.13

计算性质

• 辛醇/水分配系数(LogP)：
  2.48
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  43.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-methoxy-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indole 在 salcomine 、 双氧水 、 氧气 、 sodium hydroxide 作用下， 以 四氢呋喃 、 水 、 乙腈 为溶剂， 反应 4.17h， 生成 5-methoxyindole-4,7-quinone
  参考文献：
  名称：

  Iridium-Catalyzed C–H Borylation-Based Synthesis of Natural Indolequinones

  摘要：

  An iridium-catalyzed C-H borylation provides the key step in a short synthesis of two indolequinone natural products. This regioselective C-H functionalization strategy delivers 7-borylindoles that undergo facile oxidation hydrolysis to 7-hydroyindoles and subsequent oxidation to the desired indolequinones, thereby demonstrating a powerful application of the iridium-catalyzed C H borylation reaction. A significant result has arisen from the iridium-catalyzed borylation of N-diethylhydrosilyl-6-methoxyindole; even in the presence of a substituent at C6, the N-hydrosilyl group still directs borylation exclusively into the more sterically hindered C7 position in preference to C2.

  DOI：

  10.1021/jo300330u
• 作为产物：
  描述：

  在 水 、 sodium acetate 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以160 mg的产率得到5-methoxy-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indole
  参考文献：
  名称：

  Iridium-Catalyzed, Silyl-Directed Borylation of Nitrogen-Containing Heterocycles

  摘要：

  Selective methods for the functionalization of indoles and other nitrogen heterocycles would provide access to the core structures of many natural products and pharmaceuticals. Although there are many methods and strategies for the synthesis of substituted indoles or functionalization of the azole ring, strategies for the selective functionalization of the benzo-fused portion of the indole skeleton, particularly the 7-position, are less common. We report a one-pot, iridium-catalyzed, silyl-directed C-H borylation of indoles at the 7-position. This process occurs in high yield with a variety of substituted indoles, and conversions of the 7-borylindole products to 7-aryl-, 7-cinnamyl-, and 7-haloindoles are demonstrated. The Ir-catalyzed, silyl-directed C-H borylation also occurs with several other nitrogen heterocycles, including carbazole, phenothiazines, and tetrahydroquinoline. The utility of this methodology is highlighted by the one-pot synthesis of a member of the pyrrolophenanthridone class of alkaloid natural products.

  DOI：

  10.1021/ja1006405

文献信息

• Convergent Total Syntheses of the Amaryllidaceae Alkaloids Lycoranine A, Lycoranine B, and 2-Methoxypratosine
  作者：Hye Sun Kim、Martin G. Banwell、Anthony C. Willis

  DOI：10.1021/jo4006987

  日期：2013.5.17

  and 3 respectively, have been prepared in a convergent manner by two related routes. The superior one involves C–H functionalization of the relevant 5-methoxyindole at C-7 using Hartwig’s protocol and thus forming the corresponding borolated indole that could be coupled with the requisite 2-bromobenzoate to deliver the title natural products. Single crystal X-ray analyses of the synthetically derived

  标题生物碱，1，2，和3已经分别以会聚的方式通过两个相关的途径制备。上等产品涉及使用Hartwig的规程在C-7处将相关的5-甲氧基吲哚进行C–H官能化，从而形成相应的硼化吲哚，可与必需的2-溴苯甲酸酯偶联以提供标题的天然产物。报道了化合物1和2的合成衍生样品的单晶X射线分析。
• Iridium-Catalyzed, Silyl-Directed Borylation of Nitrogen-Containing Heterocycles
  作者：Daniel W. Robbins、Timothy A. Boebel、John F. Hartwig

  DOI：10.1021/ja1006405

  日期：2010.3.31

  Selective methods for the functionalization of indoles and other nitrogen heterocycles would provide access to the core structures of many natural products and pharmaceuticals. Although there are many methods and strategies for the synthesis of substituted indoles or functionalization of the azole ring, strategies for the selective functionalization of the benzo-fused portion of the indole skeleton, particularly the 7-position, are less common. We report a one-pot, iridium-catalyzed, silyl-directed C-H borylation of indoles at the 7-position. This process occurs in high yield with a variety of substituted indoles, and conversions of the 7-borylindole products to 7-aryl-, 7-cinnamyl-, and 7-haloindoles are demonstrated. The Ir-catalyzed, silyl-directed C-H borylation also occurs with several other nitrogen heterocycles, including carbazole, phenothiazines, and tetrahydroquinoline. The utility of this methodology is highlighted by the one-pot synthesis of a member of the pyrrolophenanthridone class of alkaloid natural products.
• Iridium-Catalyzed C–H Borylation-Based Synthesis of Natural Indolequinones
  作者：Christy Wang、Jonathan Sperry

  DOI：10.1021/jo300330u

  日期：2012.3.16

  An iridium-catalyzed C-H borylation provides the key step in a short synthesis of two indolequinone natural products. This regioselective C-H functionalization strategy delivers 7-borylindoles that undergo facile oxidation hydrolysis to 7-hydroyindoles and subsequent oxidation to the desired indolequinones, thereby demonstrating a powerful application of the iridium-catalyzed C H borylation reaction. A significant result has arisen from the iridium-catalyzed borylation of N-diethylhydrosilyl-6-methoxyindole; even in the presence of a substituent at C6, the N-hydrosilyl group still directs borylation exclusively into the more sterically hindered C7 position in preference to C2.