cis-3,4-dihydro-2-ethoxycarbonyl-3-(1-hexyl)-4-methylene-2H-1-benzopyran

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: cis-3,4-dihydro-2-ethoxycarbonyl-3-(1-hexyl)-4-methylene-2H-1-benzopyran
• 英文别名: ethyl (2S,3R)-3-hexyl-4-methylidene-2,3-dihydrochromene-2-carboxylate
• 化学式: C₁₉H₂₆O₃
• 分子量: 302.414
• InChiKey: AUMMQAZJQWJUBN-AEFFLSMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  、 1,2-壬二烯 在 Tentagel functionalized with p-Ph₂PC₆H₄CO₂H 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 (E)-3,4-dihydro-2-ethoxycarbonyl-4-(heptylidene)-2H-1-benzopyran 、 cis-3,4-dihydro-2-ethoxycarbonyl-3-(1-hexyl)-4-methylene-2H-1-benzopyran
  参考文献：
  名称：

  Polymer-Supported Palladacycles:  Efficient Reagents for Synthesis of Benzopyrans with Palladium Recovery. Relationship among Resin Loading, Pd:P Ratio, and Reactivity of Immobilized Palladacycles

  摘要：

  Oxapalladacycles were immobilized on polystyrene-divinylbenzene supports and treated with 3-aryl-2-propynoates or 1-alkyl-1,2-propadienes to afford 2H-1-benzopyrans in yields superior to those for solution-phase experiments. Isolation of benzopyrans was facilitated, and 71-80% of the palladium was recovered. Effects of resin loading with phosphorus and palladium were studied, and the optimum immobilized palladacycles featuring a medium loading with P (1.35 mmol P/g) and a high loading with Pd (Pd:P ratio 1: 1.7) were identified. Resins with higher swelling capacities were more reactive.

  DOI：

  10.1021/jo052105w

文献信息

• Regio- and Diastereoselective Insertion of Allenes into Stable Oxapalladacycles with a Metal-Bonded Stereogenic Carbon. Preparation of Contiguously Substituted 3,4-Dihydro-2<i>H</i>-1-Benzopyrans
  作者：Genliang Lu、Helena C. Malinakova

  DOI：10.1021/jo0486847

  日期：2004.11.1

  2-propadiene afforded benzopyran IV in 98% yield as the trans diastereomer in 92% de. In contrast, allenes with electron-withdrawing substituents yielded benzopyrans V with an E double bond exclusively. Nonracemic palladacycles featuring a palladium-bonded stereogenic carbon as the only element of asymmetry underwent the allene insertion with 63−93% retention of the stereochemical information, providing benzopyrans

  研究了将单取代的异戊烯插入稳定的氧杂四环四环Ⅰ中。这项工作的目的是定义能够实现2,3-二取代的3,4-二氢-2 H -1-苯并吡喃的区域和非对映选择性合成的异戊二烯的空间和电子参数，而这不能通过相关方法制备。催化方案。在C-3和C-4碳上空间不受限的具有供电子性烷基取代基R的丙二烯与palladacycles I反应，以良好的收率（45-81％）提供苯并吡喃IV，仅作为顺式非对映异构体。在粗反应混合物中检测不到少于10％的区域异构苯并吡喃V。甲氧基1,2-丙二烯制得的苯并吡喃IV的产率为98％，反式非对映体的产率为92％。相比之下，具有吸电子取代基的丙二烯仅产生具有E双键的苯并吡喃V。以钯键合立体异构碳为非对称性唯一元素的非外消旋palladacycles进行了丙二烯插入，保留了63-93％的立体化学信息，从而提供了苯并吡喃IV或V在40−47％ee中。这些结果表明，O-键合的烯醇钯在插入
• Polymer-Supported Palladacycles:  Efficient Reagents for Synthesis of Benzopyrans with Palladium Recovery. Relationship among Resin Loading, Pd:P Ratio, and Reactivity of Immobilized Palladacycles
  作者：John C. Hershberger、Lei Zhang、Genliang Lu、Helena C. Malinakova

  DOI：10.1021/jo052105w

  日期：2006.1.1

  Oxapalladacycles were immobilized on polystyrene-divinylbenzene supports and treated with 3-aryl-2-propynoates or 1-alkyl-1,2-propadienes to afford 2H-1-benzopyrans in yields superior to those for solution-phase experiments. Isolation of benzopyrans was facilitated, and 71-80% of the palladium was recovered. Effects of resin loading with phosphorus and palladium were studied, and the optimum immobilized palladacycles featuring a medium loading with P (1.35 mmol P/g) and a high loading with Pd (Pd:P ratio 1: 1.7) were identified. Resins with higher swelling capacities were more reactive.