(Z)-ethyl 2,4-bis(benzyloxy)-5-methoxy-α-nitrocinnamate | 1034028-91-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (Z)-ethyl 2,4-bis(benzyloxy)-5-methoxy-α-nitrocinnamate
• 英文别名: ethyl 3-(2,4-bisbenzyloxy-5-methoxyphenyl)-2-nitroacrylate；ethyl (Z)-3-[5-methoxy-2,4-bis(phenylmethoxy)phenyl]-2-nitroprop-2-enoate
• CAS: 1034028-91-5
• 化学式: C₂₆H₂₅NO₇
• 分子量: 463.487
• InChiKey: COSKFZCOMJUPEZ-HMAPJEAMSA-N

物化性质

• 熔点：
  136-137 °C(Solv: ligroine (8032-32-4))
• 沸点：
  628.6±55.0 °C(Predicted)
• 密度：
  1.242±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  99.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (Z)-ethyl 2,4-bis(benzyloxy)-5-methoxy-α-nitrocinnamate 在 palladium on activated charcoal 氢气 、 sodium hydride 、 碳酸氢钠 作用下， 以 四氢呋喃 、 乙酸乙酯 、 乙腈 为溶剂， 20.0 ℃ 、517.11 kPa 条件下， 反应 18.0h， 生成 lamellarin 501
  参考文献：
  名称：

  Total Synthesis of Natural and Unnatural Lamellarins with Saturated and Unsaturated D-Rings

  摘要：

  Twenty-eight natural and unnatural lamellarins with either a saturated or an unsaturated D-ring were synthesized according to our developed synthetic route. The key step involved the Michael addition/ring closure (Mi-RC) of the benzyldihydroisoquinoline and alpha-nitrocinnamate derivatives, which provided the 2-carboethoxypyrrole intermediates in moderate to good yields (up to 78% yield). Subsequent hydrogenolysis/lactonization furnished lamellarins with a saturated D-ring in excellent yields (up to 93% yield). DDQ oxidation of the saturated lamellarin acetates led directly to the corresponding unsaturated analogues in 54-95% yield. In addition, only two steps in our developed strategy require column chromatography.

  DOI：

  10.1021/jo061810h
• 作为产物：
  描述：

  硝基乙酸乙酯 、 2,4-bis-(benzyloxy)-5-methoxybenzaldehyde 在 二乙胺盐酸盐 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以67%的产率得到(Z)-ethyl 2,4-bis(benzyloxy)-5-methoxy-α-nitrocinnamate
  参考文献：
  名称：

  Utility of Polymer-Supported Reagents in the Total Synthesis of Lamellarins

  摘要：

  Four solid-supported reagents have been utilized in the multistep synthesis of lamellarins. The use of Amberlyst A-26 Br-3(-) and polymer bound pyridine hydrobromide perbromide (PVPHP) for keto alpha-bromination of the less studied ortho-substituted acetophenone derivatives selectively furnished the corresponding monobromination products (phenacyl bromide derivatives), which were used directly in condensation reactions with benzyldihydroisoquinoline mediated by Amberlyst A-26 NaCO3-. The 2H-pyrrole carbonates subsequently underwent intramolecular Friedel-Crafts transacylation followed by lactonization to provide the lamellarin skeleton. Alternatively, Amberlyst A-26 NaCO3- effectively served as base in condensation reaction of benzyldihydroisoquinoline with alpha-nitrocinnamate derivatives to provide the corresponding 2-ethoxycarbonyl pyrroles, which smoothly underwent O-debenzylation reaction followed by lactonization to furnish the lamellarin skeleton. The novel Amberlyst-15 mediated lactonization reactions effectively combined the otherwise two separate steps into a single transformation.

  DOI：

  10.1021/jo050388m

文献信息

• Synthesis of Lamellarin U and Lamellarin G Trimethyl Ether by Alkylation of a Deprotonated α-Aminonitrile
  作者：Johannes C. Liermann、Till Opatz

  DOI：10.1021/jo800467e

  日期：2008.6.1

  1,2,3,4-Tetrahydroisoquinoline-1-carbonitriles can serve as starting materials for the one-pot synthesis of 5,6-dihydropyrrolo[2,1a]isoquinolines and 1-benzyl-3,4-dihydroisoquinolines. The latter compounds were transformed to lamellarin G trimethyl ether and lamellarin U in short reaction sequences. This method allows the introduction of acid-sensitive protecting groups for the phenolic hydroxy functions

  1,2,3,4-四氢异喹啉-1-腈可以用作起始的一锅合成5,6-二氢吡咯并[2,1的材料一]异喹啉和1-苄基-3,4-二氢异喹啉。后面的化合物以短的反应顺序被转化为薄片蛋白G三甲醚和薄片蛋白U。这种方法允许引入用于酚羟基官能团的酸敏感保护基，该保护基在经典的Bischler-Napieralski反应的苛刻条件下会裂解。
• A Highly Efficient Synthesis of Lamellarins K and L by the Michael Addition/Ring-Closure Reaction of Benzyldihydroisoquinoline Derivatives with Ethoxycarbonyl-β-nitrostyrenes
  作者：Poonsakdi Ploypradith、Chulabhorn Mahidol、Poolsak Sahakitpichan、Siriporn Wongbundit、Somsak Ruchirawat

  DOI：10.1002/anie.200352043

  日期：2004.2.6
• Total Synthesis of Natural and Unnatural Lamellarins with Saturated and Unsaturated D-Rings
  作者：Poonsakdi Ploypradith、Thaninee Petchmanee、Poolsak Sahakitpichan、Nichole D. Litvinas、Somsak Ruchirawat

  DOI：10.1021/jo061810h

  日期：2006.12.1

  Twenty-eight natural and unnatural lamellarins with either a saturated or an unsaturated D-ring were synthesized according to our developed synthetic route. The key step involved the Michael addition/ring closure (Mi-RC) of the benzyldihydroisoquinoline and alpha-nitrocinnamate derivatives, which provided the 2-carboethoxypyrrole intermediates in moderate to good yields (up to 78% yield). Subsequent hydrogenolysis/lactonization furnished lamellarins with a saturated D-ring in excellent yields (up to 93% yield). DDQ oxidation of the saturated lamellarin acetates led directly to the corresponding unsaturated analogues in 54-95% yield. In addition, only two steps in our developed strategy require column chromatography.
• Utility of Polymer-Supported Reagents in the Total Synthesis of Lamellarins
  作者：Poonsakdi Ploypradith、Rachel Kirk Kagan、Somsak Ruchirawat

  DOI：10.1021/jo050388m

  日期：2005.6.1

  Four solid-supported reagents have been utilized in the multistep synthesis of lamellarins. The use of Amberlyst A-26 Br-3(-) and polymer bound pyridine hydrobromide perbromide (PVPHP) for keto alpha-bromination of the less studied ortho-substituted acetophenone derivatives selectively furnished the corresponding monobromination products (phenacyl bromide derivatives), which were used directly in condensation reactions with benzyldihydroisoquinoline mediated by Amberlyst A-26 NaCO3-. The 2H-pyrrole carbonates subsequently underwent intramolecular Friedel-Crafts transacylation followed by lactonization to provide the lamellarin skeleton. Alternatively, Amberlyst A-26 NaCO3- effectively served as base in condensation reaction of benzyldihydroisoquinoline with alpha-nitrocinnamate derivatives to provide the corresponding 2-ethoxycarbonyl pyrroles, which smoothly underwent O-debenzylation reaction followed by lactonization to furnish the lamellarin skeleton. The novel Amberlyst-15 mediated lactonization reactions effectively combined the otherwise two separate steps into a single transformation.