tert-Butyl (E)-2-((4-Hydroxy-3-methoxyphenyl)methyl)-3-oxo-4-decenoate | 145822-71-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: tert-Butyl (E)-2-((4-Hydroxy-3-methoxyphenyl)methyl)-3-oxo-4-decenoate
• 英文别名: tert-butyl (E)-2-[(4-hydroxy-3-methoxyphenyl)methyl]-3-oxodec-4-enoate
• CAS: 145822-71-5
• 化学式: C₂₂H₃₂O₅
• 分子量: 376.493
• InChiKey: BJHQAEFMEJCZGF-ZHACJKMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  27
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-Butyl (E)-2-((4-Hydroxy-3-methoxyphenyl)methyl)-3-oxo-4-decenoate 在 三氟乙酸 作用下， 以 苯 为溶剂， 反应 2.0h， 生成 [6]-shogaol
  参考文献：
  名称：

  Synthesis of α,β-Unsaturated Ketones Using Allylidenetriphenylphosphorane as a Three-carbon Unit

  摘要：

  在碱存在下，3-烷氧羰基-2-乙氧基-2-亚丙烯基三苯基膦通过一锅程序依次与烷基卤化物和醛发生反应，生成中等至高产率的共轭烯醇醚。共轭烯醇醚的水解和随后的脱羧反应提供了一种获得 α、β-不饱和酮的新途径。

  DOI：

  10.1246/cl.1992.2253
• 作为产物：
  描述：

  2-甲氧基-4-甲基苯酚 在 咪唑 、 N-溴代丁二酰亚胺(NBS) 、 硫酸 、 silica gel 、 caesium carbonate 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 96.0h， 生成 tert-Butyl (E)-2-((4-Hydroxy-3-methoxyphenyl)methyl)-3-oxo-4-decenoate
  参考文献：
  名称：

  Synthesis of α,β-Unsaturated Ketones Using Allylidenetriphenylphosphorane as a Three-carbon Unit

  摘要：

  在碱存在下，3-烷氧羰基-2-乙氧基-2-亚丙烯基三苯基膦通过一锅程序依次与烷基卤化物和醛发生反应，生成中等至高产率的共轭烯醇醚。共轭烯醇醚的水解和随后的脱羧反应提供了一种获得 α、β-不饱和酮的新途径。

  DOI：

  10.1246/cl.1992.2253

文献信息

• Synthesis of α,β-Unsaturated Ketones Using Allylidenetriphenylphosphorane as a Three-carbon Unit
  作者：Minoru Hatanaka、Ritsuo Imashiro、Ikuo Ueda

  DOI：10.1246/cl.1992.2253

  日期：1992.11

  3-Alkoxycarbonyl-2-ethoxy-2-propenylidenetriphenylphosphorane reacts in turn with alkyl halides and aldehydes in the presence of base via a one-pot procedure to give moderate to good yields of conjugated enol ethers. Hydrolysis of the conjugated enol ethers and subsequent decarboxylation provide a novel route to α,β-unsaturated ketones.

  在碱存在下，3-烷氧羰基-2-乙氧基-2-亚丙烯基三苯基膦通过一锅程序依次与烷基卤化物和醛发生反应，生成中等至高产率的共轭烯醇醚。共轭烯醇醚的水解和随后的脱羧反应提供了一种获得 α、β-不饱和酮的新途径。
• Allylidenetriphenylphosphorane as a bifunctional reagent: synthesis of cyclopentenones and .alpha.,.beta.-unsaturated ketones with [3-(alkoxycarbonyl)-2-ethoxy-2-propenylidene]triphenylphosphorane
  作者：Minoru Hatanaka、Yuichiro Himeda、Ritsuo Imashiro、Yasuhiro Tanaka、Ikuo Ueda

  DOI：10.1021/jo00080a019

  日期：1994.1

  When (3-(ethoxycarbonyl)-2-ethoxy-2-propenylidene) triphenylphosphorane (6) was allowed to react with cu-bromo ketones 8a-d in dichloromethane in the presence of Cs2CO3 at room temperature, a [3 + 2] annulation occurred and led to the formation of the corresponding 2-ethoxycyclopentadienes 9a-d in excellent yields. Similarly, bromo thioester 8g underwent the annulation to give 4-(ethylthio)-cyclopentadiene 9g. Secondary bromides 2-bromo-3-pentanone and 2-bromocyclohexanone also afforded tetrasubstituted cyclopentadienes 9e and 9f in moderate yields when 2 equiv of 6 was used. The annulation is believed to proceed through a sequence involving a stepwise alkylation at the gamma position of 6 and an intramolecular Wittig reaction because of the fact that intermediate 11 was isolated. The resulting 2-ethoxycyclopentadienes 9a-g were converted quantitatively into the corresponding cyclopentenones 10a-g upon mild acid treatment. Furthermore, allylidenetriphenylphosphorane underwent a carbon elongation at both ends of the three-carbon unit via an alkylation-Wittig reaction sequence. (3-(tert-Butoxycarbonyl)-2-ethoxy-2-propenylidene)triphenylphosphorane (7) reacted first with alkyl halides and then with aldehydes in the presence of Cs2CO3 to give enol ethers 23a-f, which were converted into alpha,beta-unsaturated ketones 20, 21, and 25c-f by hydrolysis of the enol ether and then decarboxylation. In this way, shogaol (29), the pungent principle component of ginger, was conveniently synthesized starting from 2-methoxy-4-methylphenol.