2-(1-Adamantyl)ethynyl bromide | 259546-36-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代乙炔及其衍生物
• 英文名称: 2-(1-Adamantyl)ethynyl bromide
• 英文别名: 1-(2-Bromoethynyl)adamantane；1-(2-bromoethynyl)adamantane
• CAS: 259546-36-6
• 化学式: C₁₂H₁₅Br
• 分子量: 239.155
• InChiKey: WEPVFPCFCBMMEP-UHFFFAOYSA-N

物化性质

• 熔点：
  130-133 °C
• 沸点：
  286.6±23.0 °C(predicted)
• 密度：
  1.41±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-(1-Adamantyl)ethynyl bromide 在 盐酸羟胺 、 正丁胺 、 copper(l) chloride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 2-(1-Adamantyl)-3-[2-[3-(1-adamantyl)-4-hydroxy-1-methoxy-5,6,7,8-tetrahydronaphthalen-2-yl]ethynyl]-4-methoxy-5,6,7,8-tetrahydronaphthalen-1-ol
  参考文献：
  名称：

  Contingency and Serendipity in the Reactions of Fischer Carbene Complexes with Conjugated Triynes

  摘要：

  The first examples of reactions of Fischer carbene complexes with triynes are reported. The regioselectivity of the reaction of the two different alkyne functions in the symmetrical triyne depends on the nature of the substituent of the triyne. Bis-silyl-substituted triynes react at the central alkyne unit, whereas bis-aryl- and bis-alkyl-substituted triynes react at the end alkyne unit. The reaction of a Fischer carbene complex with a phenyl substituent also reacts with a bis-silyl-substituted triyne at the central alkyne unit but gives a furan product rather than the normal phenol product. It was also demonstrated that all three of the alkyne units in conjugated triynes could react in turn with a Fischer carbene complex to give access to trisquinones.

  DOI：

  10.1021/ja049836i
• 作为产物：
  描述：

  1-乙炔基金刚烷 在 N-溴代丁二酰亚胺(NBS) 、 silver nitrate 作用下， 以 丙酮 为溶剂， 反应 2.0h， 以89%的产率得到2-(1-Adamantyl)ethynyl bromide
  参考文献：
  名称：

  Contingency and Serendipity in the Reactions of Fischer Carbene Complexes with Conjugated Triynes

  摘要：

  The first examples of reactions of Fischer carbene complexes with triynes are reported. The regioselectivity of the reaction of the two different alkyne functions in the symmetrical triyne depends on the nature of the substituent of the triyne. Bis-silyl-substituted triynes react at the central alkyne unit, whereas bis-aryl- and bis-alkyl-substituted triynes react at the end alkyne unit. The reaction of a Fischer carbene complex with a phenyl substituent also reacts with a bis-silyl-substituted triyne at the central alkyne unit but gives a furan product rather than the normal phenol product. It was also demonstrated that all three of the alkyne units in conjugated triynes could react in turn with a Fischer carbene complex to give access to trisquinones.

  DOI：

  10.1021/ja049836i

文献信息

• Sterically Controlled Late-Stage C–H Alkynylation of Arenes
  作者：Arup Mondal、Hao Chen、Lea Flämig、Philipp Wedi、Manuel van Gemmeren

  DOI：10.1021/jacs.9b10868

  日期：2019.11.27

  Phenylacetylenes are key structural motifs in organic chemistry, which find widespread applications in bioactive molecules, synthetic intermediates, functional materials and reagents. These molecules are typically prepared from pre-functionalized starting materials, e.g. using the Sonogashira coupling, or using directing group-based C-H activation strategies. While highly efficient, these approaches

  苯乙炔是有机化学中的关键结构基序，广泛应用于生物活性分子、合成中间体、功能材料和试剂。这些分子通常由预官能化的起始材料制备，例如使用 Sonogashira 偶联，或使用基于导向基团的 CH 活化策略。虽然效率很高，但这些方法仍然受到它们对特定区域异构体的固有选择性的限制。在此，我们提出了一种基于芳烃限制的非定向 CH 激活的补充方法。该反应主要受空间因素而非电子因素的控制，从而提供了相对于传统方法的互补产品谱。
• Catalyst‐Controlled Regiodivergent C−H Alkynylation of Thiophenes**
  作者：Arup Mondal、Manuel Gemmeren

  DOI：10.1002/anie.202012103

  日期：2021.1.11

  the thiophenes studied herein, consists of a halogenation followed by a Sonogashira cross‐coupling. The regioselectivity of this approach depends entirely on the halogenation step. Similarly, direct alkynylations of thiophenes have been described that follow the same regioselectivity patterns. Herein we report the development of a palladium catalyzed C−H activation/alkynylation of thiophenes. The method

  炔烃在有机合成中是极具吸引力的基序，因为它们存在于天然产物和生物活性分子中，并且在大量后续转化中具有多功能性。将炔烃插入（杂）芳烃（例如本文研究的噻吩）的常见程序包括卤化，然后是 Sonogashira 交叉偶联。该方法的区域选择性完全取决于卤化步骤。类似地，噻吩的直接炔基化也遵循相同的区域选择性模式。在此，我们报告了钯催化噻吩的 C−H 活化/炔基化的进展。该方法适用于广泛的噻吩底物。对于控制 C2 和 C5 位置之间的区域选择性特别具有挑战性的 3 取代底物，两组反应条件可实现区域发散反应，从而选择性地获得每种区域异构体。两种方案都使用噻吩作为限制试剂，并且显示出广泛的范围，使我们的方法适合后期修改。
• Mueller, Torsten; Hulliger, Juerg; Seichter, Wilhelm, Chemistry - A European Journal, 2000, vol. 6, # 1, p. 54 - 61
  作者：Mueller, Torsten、Hulliger, Juerg、Seichter, Wilhelm、Weber, Edwin、Weber, Thomas、Wuebbenhorst, Michael

  DOI：——

  日期：——
• Contingency and Serendipity in the Reactions of Fischer Carbene Complexes with Conjugated Triynes
  作者：May Xiao-Wu Jiang、Manish Rawat、William D. Wulff

  DOI：10.1021/ja049836i

  日期：2004.5.1

  The first examples of reactions of Fischer carbene complexes with triynes are reported. The regioselectivity of the reaction of the two different alkyne functions in the symmetrical triyne depends on the nature of the substituent of the triyne. Bis-silyl-substituted triynes react at the central alkyne unit, whereas bis-aryl- and bis-alkyl-substituted triynes react at the end alkyne unit. The reaction of a Fischer carbene complex with a phenyl substituent also reacts with a bis-silyl-substituted triyne at the central alkyne unit but gives a furan product rather than the normal phenol product. It was also demonstrated that all three of the alkyne units in conjugated triynes could react in turn with a Fischer carbene complex to give access to trisquinones.