5-(1-methyl-2-propen-1-yl)-1H-indole-1-carboxylic acid 1,1-dimethylethyl ester | 1092390-65-2

• 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-(1-methyl-2-propen-1-yl)-1H-indole-1-carboxylic acid 1,1-dimethylethyl ester
• 英文别名: 5-(1-methyl-2-propen-1-yl)1H-indole-1-carboxylic acid 1,1-dimethylethyl ester；Tert-butyl 5-but-3-en-2-ylindole-1-carboxylate；tert-butyl 5-but-3-en-2-ylindole-1-carboxylate
• CAS: 1092390-65-2
• 化学式: C₁₇H₂₁NO₂
• 分子量: 271.359
• InChiKey: JMWIUMBHTYDICT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  31.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  sodium (Z)-2-buten-1-yl-diethylsilanolate 、 N-叔丁氧羰基-5-溴吲哚 在 t-BuCy2PH(+)BF4(-) 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 甲苯 为溶剂， 以91%的产率得到5-(1-methyl-2-propen-1-yl)-1H-indole-1-carboxylic acid 1,1-dimethylethyl ester
  参考文献：
  名称：

  使用由膦•硼烷加合物直接制备的三烷基鏻四氟硼酸盐对烯丙基硅烷醇盐与芳族溴化物的 γ-选择性交叉偶联

  摘要：

  报道了γ 选择性、钯催化的 ( Z )-2-丁烯基二乙基硅烷醇钠与多种芳香族溴化物的交叉偶联。该协议在富电子、缺电子、空间位阻和杂芳族溴化物的耦合中提供了高产率 (73–94%) 和位点选择性 (γ/α, 25:1 → > 99:1)。使用由相应的空气稳定膦•硼烷加合物直接制备的构型均匀的 ( Z )-硅烷醇化物、不可转移的乙基和空间庞大的三烷基鏻四氟硼酸盐 ( t -BuCy 2 PH + BF 4 – ) 对方法的成功。

  DOI：

  10.1021/ol2017998

文献信息

• Cross-Coupling of Aromatic Bromides with Allylic Silanolate Salts
  作者：Scott E. Denmark、Nathan S. Werner

  DOI：10.1021/ja805951j

  日期：2008.12.3

  The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85 degrees C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (gamma-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher gamma-selectivity than the pure (2)-silanolates. A unified mechanistic picture involving initial gamma-transmetalation followed by direct reductive elimination or sigma-pi isomerization can rationalize all of the observed trends.
• γ-Selective Cross-Coupling of Allylic Silanolate Salts with Aromatic Bromides Using Trialkylphosphonium Tetrafluoroborate Salts Prepared Directly from Phosphine•Borane Adducts
  作者：Scott E. Denmark、Nathan S. Werner

  DOI：10.1021/ol2017998

  日期：2011.9.2

  γ-selective, palladium-catalyzed cross-coupling of sodium (Z)-2-butenyldiethylsilanolate with a variety of aromatic bromides is reported. The protocol provides high yields (73–94%) and site selectivity (γ/α, 25:1 → > 99:1) in the coupling of electron-rich, electron-poor, sterically hindered, and heteroaromatic bromides. The use of a configurationally homogeneous (Z)-silanolate, nontransferable ethyl groups

  报道了γ 选择性、钯催化的 ( Z )-2-丁烯基二乙基硅烷醇钠与多种芳香族溴化物的交叉偶联。该协议在富电子、缺电子、空间位阻和杂芳族溴化物的耦合中提供了高产率 (73–94%) 和位点选择性 (γ/α, 25:1 → > 99:1)。使用由相应的空气稳定膦•硼烷加合物直接制备的构型均匀的 ( Z )-硅烷醇化物、不可转移的乙基和空间庞大的三烷基鏻四氟硼酸盐 ( t -BuCy 2 PH + BF 4 – ) 对方法的成功。