2,4-di-tert-butyl-6-ethynyl-(2-propenyloxy)benzene | 359011-24-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,4-di-tert-butyl-6-ethynyl-(2-propenyloxy)benzene
• 英文别名: 4,6-di-tert-butyl-2-ethynyl-(2-propenyloxy)benzene；1,5-Ditert-butyl-3-ethynyl-2-prop-2-enoxybenzene
• CAS: 359011-24-8
• 化学式: C₁₉H₂₆O
• 分子量: 270.415
• InChiKey: AVHVIHOAHZDSNF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  2,4-di-tert-butyl-6-ethynyl-(2-propenyloxy)benzene 、 alkaline earth salt of/the/ methylsulfuric acid 以 甲苯 为溶剂， 反应 5.0h， 以91%的产率得到6,8-di-tert-butyl-3a,4-dihydro-3H-cyclopenta[c]chromen-2-one
  参考文献：
  名称：

  Steric buttressing in the Pauson–Khand reactions of aryl enynes

  摘要：

  A variety of aryl enynes have been constructed from o-iodophenol derivatives containing ortho-tert-butyl groups via O-alkylation and a Sonogashira cross-coupling reaction. These substrates undergo efficient thermal and oxidative intramolecular Pauson-Khand reactions leading to the formation of sterically congested cyclopentenones, as well as the formation of medium-sized rings, although in the latter case with unusual regioselectivity. Incorporation of a TMS moiety on the alkyne group in a higher homolog led to cyclization via the normal mode, albeit in relatively low yield. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.03.131
• 作为产物：
  描述：

  2,4-二叔丁基苯酚 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 碘 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 丙酮 为溶剂， 反应 5.0h， 生成 2,4-di-tert-butyl-6-ethynyl-(2-propenyloxy)benzene
  参考文献：
  名称：

  Synthesis of Bridged Medium-Sized Rings through the Intramolecular Pauson−Khand Reaction

  摘要：

  [GRAPHICS]A series of aromatic enynes containing steric buttressing elements were prepared and evaluated in the NMO-mediated Pauson-Khand cyclization. O-Allyl systems led to the expected angularly fused products, whereas the O-butenyl and O-pentenyl derivatives afforded the unprecedented bridge systems.

  DOI：

  10.1021/ol016308s

文献信息

• Steric buttressing in the Pauson-Khand reactions of benzyl enynes
  作者：Christian E. Madu、H.V. Rasika Dias、Carl J. Lovely

  DOI：10.1016/j.tet.2017.08.053

  日期：2017.10

  the former case, the diastereoselectivities are high. An investigation of the tolerance of this cycloaddition to substitution around the 1,8-enyne demonstrates that only 2,2-disubstitution does not result in productive cyclization. Cycloadditions with hydroxyl groups at the propargylic position while leading to fused rings are compromised by side reactions leading to reduction and in some cases tautomerization

  1，n-烯炔的分子内Pauson-Khand反应的应用为构建多环骨架提供了一种方便的方法，但该过程在很大程度上限于5,5-和5,6-稠合环体系的形成。在本报告中，我们描述了Pauson-Khand环化对嵌入芳香环系统中的1,8-烯炔的应用，其中确定存在以t形式存在的空间扶壁丁基有助于环加成。这些反应通过热活化或氧化活化都能以高收率进行，在前一种情况下，非对映选择性很高。对这种环加成反应对1,8-烯炔的耐受性的研究表明，只有2,2-二取代不会导致生产性环化。在导致稠合环的同时在炔丙基位置具有羟基的环加成反应会受到副反应的损害，从而导致还原反应和某些情况下的互变异构。然而，通过羟基转化为相应的甲硅烷基醚，可以容易地使这些副产物最小化。
• Silaborative Carbocyclizations of 1,7-Enynes. Diastereoselective Preparation of Chromane Derivatives
  作者：You-Cai Xiao、Christina Moberg

  DOI：10.1021/acs.orglett.5b03479

  日期：2016.1.15

  Palladium(0)-catalyzed carbocyclization of 1,7-enynes mediated by (chlorodimethylsilyl)pinacolborane proceeds with 1,8-addition of the silicon and boron functions to give functionalized cyclohexane derivatives with boron attached to the exocyclic olefin. A variety of chromane dervatives are accessible by this method. In contrast to the analogous reactions with 1,6-enynes, the configuration of the newly

  由（氯二甲基甲硅烷基）频哪烷硼烷介导的钯（0）催化1,7-炔烃的碳环化反应是通过1,8-加成硅和硼官能进行的，得到官能化的环己烷衍生物，其中硼连接到环外烯烃上。通过该方法可得到各种苯并二氢吡喃衍生物。与与1，6-烯炔的类似反应相反，新形成的立体异构中心的构型由底物中存在的立体异构中心控制。
• Synthesis of Bridged Medium-Sized Rings through the Intramolecular Pauson−Khand Reaction
  作者：Carl J. Lovely、Hemalatha Seshadri、Brian R. Wayland、A. Wallace Cordes

  DOI：10.1021/ol016308s

  日期：2001.8.9

  [GRAPHICS]A series of aromatic enynes containing steric buttressing elements were prepared and evaluated in the NMO-mediated Pauson-Khand cyclization. O-Allyl systems led to the expected angularly fused products, whereas the O-butenyl and O-pentenyl derivatives afforded the unprecedented bridge systems.
• Steric buttressing in the Pauson–Khand reactions of aryl enynes
  作者：Christian E. Madu、Hemalatha Seshadri、Carl J. Lovely

  DOI：10.1016/j.tet.2007.03.131

  日期：2007.6

  A variety of aryl enynes have been constructed from o-iodophenol derivatives containing ortho-tert-butyl groups via O-alkylation and a Sonogashira cross-coupling reaction. These substrates undergo efficient thermal and oxidative intramolecular Pauson-Khand reactions leading to the formation of sterically congested cyclopentenones, as well as the formation of medium-sized rings, although in the latter case with unusual regioselectivity. Incorporation of a TMS moiety on the alkyne group in a higher homolog led to cyclization via the normal mode, albeit in relatively low yield. (c) 2007 Elsevier Ltd. All rights reserved.