[1-(3-hydroxy-5-methoxy-phenyl)-cyclohexa-2,5-dienyl]-acetic acid methyl ester | 912580-93-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: [1-(3-hydroxy-5-methoxy-phenyl)-cyclohexa-2,5-dienyl]-acetic acid methyl ester
• 英文别名: Methyl 2-[1-(3-hydroxy-5-methoxyphenyl)cyclohexa-2,5-dien-1-yl]acetate
• CAS: 912580-93-9
• 化学式: C₁₆H₁₈O₄
• 分子量: 274.317
• InChiKey: WCXOJWLWWLTNOO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [1-(3-hydroxy-5-methoxy-phenyl)-cyclohexa-2,5-dienyl]-acetic acid methyl ester 在 sodium tetrahydroborate 、 二异丁基氢化铝 、 potassium carbonate 、 sodium sulfate 作用下， 以 甲醇 、 正己烷 、 二氯甲烷 、 丙酮 、 甲苯 为溶剂， 反应 22.0h， 生成 {2-[1-(3,5-dimethoxy-phenyl)-cyclohexa-2,5-dienyl]-ethyl}-(2-methoxy-1-phenyl-ethyl)-amine
  参考文献：
  名称：

  Desymmetrization of Cyclohexa-2,5-dienes through a Diastereoselective Protonation−Hydroamination Cascade

  摘要：

  Intramolecular hydroamination of cyclohexa-2,5-dienes led with high selectivity to the corresponding bicyclic allylic amines. This study demonstrates that the reaction does not proceed through a direct hydroamination of one of the diastereotopic olefins but more likely involves a diastereoselective protonation of a pentadienyl anion, followed by addition of a lithium amide across the double bond of the resulting 1,3-diene, and is concluded by a highly regioselective protonation of the final allylic anion.

  DOI：

  10.1021/ol0618353
• 作为产物：
  描述：

  3-hydroxy-5-methoxybiphenyl 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.42h， 生成 [1-(3-hydroxy-5-methoxy-phenyl)-cyclohexa-2,5-dienyl]-acetic acid methyl ester
  参考文献：
  名称：

  Desymmetrization of Cyclohexa-2,5-dienes through a Diastereoselective Protonation−Hydroamination Cascade

  摘要：

  Intramolecular hydroamination of cyclohexa-2,5-dienes led with high selectivity to the corresponding bicyclic allylic amines. This study demonstrates that the reaction does not proceed through a direct hydroamination of one of the diastereotopic olefins but more likely involves a diastereoselective protonation of a pentadienyl anion, followed by addition of a lithium amide across the double bond of the resulting 1,3-diene, and is concluded by a highly regioselective protonation of the final allylic anion.

  DOI：

  10.1021/ol0618353

文献信息

• Birch Reductive Alkylation of Biaryls: Scope and Limitations
  作者：Raphaël Lebeuf、Julie Dunet、Redouane Beniazza、Dawood Ibrahim、Gopal Bose、Muriel Berlande、Frédéric Robert、Yannick Landais

  DOI：10.1021/jo901395m

  日期：2009.9.4

  5-dimethoxyphenyl moiety and a phenol ring may, however, be reduced and alkylated provided the acidic phenolic proton is removed prior to the treatment with Li in NH3. Similarly, biaryls possessing a o-sulfonamide group are reduced regioselectively and alkylated with α-chloroacetonitrile or N-tosylaziridine to provide the corresponding dienes in reasonable to good yields. A survey of the alkylating agents was also

  通过改变芳环上取代基的性质，进行了联芳基的桦树还原性烷基化。我们的研究集中在富含电子的取代基（例如OMe，OH和NR 2基团）上，因为它们存在于目标生物碱的骨架上。区域选择性受两个环上这些取代基的电子性质的强烈影响。3，5-二甲氧基苯基部分被选择性还原然后烷基化，而苯酚和苯胺在这些条件下不发生反应。但是，只要在用Li在NH 3中处理之前除去酸性酚质子，就可以还原同时具有3，5-二甲氧基苯基部分和酚环的联芳基并烷基化。类似地，联芳基化合物具有一个Ô-磺酰胺基区域选择性地还原，并用α-氯乙腈或N-甲苯磺酰基氮丙啶烷基化，以合理至良好的产率提供相应的二烯。还对烷基化剂进行了调查，结果表明可以在苄基位置引入各种官能团，包括酯，伯和叔酰胺，腈，环氧化物和乙缩醛，以及未官能化的空间位阻t- Bu基和环丙基取代基。引入后者的表示两个A S Ñ 2和SET机构可以在所述烷基化步骤进行。
• Desymmetrization of Cyclohexa-2,5-dienes through a Diastereoselective Protonation−Hydroamination Cascade
  作者：Raphaël Lebeuf、Frédéric Robert、Kurt Schenk、Yannick Landais

  DOI：10.1021/ol0618353

  日期：2006.10.1

  Intramolecular hydroamination of cyclohexa-2,5-dienes led with high selectivity to the corresponding bicyclic allylic amines. This study demonstrates that the reaction does not proceed through a direct hydroamination of one of the diastereotopic olefins but more likely involves a diastereoselective protonation of a pentadienyl anion, followed by addition of a lithium amide across the double bond of the resulting 1,3-diene, and is concluded by a highly regioselective protonation of the final allylic anion.