ethyl 1-(3,4-dimethoxyphenyl)-2-(2-benzyloxy-4,5-dimethoxyphenyl)-8,9-dimethoxy-5,6-dihydropyrrolo[2,1-a]isoquinoline-3-carboxylate | 858520-96-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: ethyl 1-(3,4-dimethoxyphenyl)-2-(2-benzyloxy-4,5-dimethoxyphenyl)-8,9-dimethoxy-5,6-dihydropyrrolo[2,1-a]isoquinoline-3-carboxylate
• 英文别名: ethyl 2-(2-benzyloxy-4,5-dimethoxyphenyl)-8,9-dimethoxy-1-(3,4-dimethoxyphenyl)-5,6-dihydropyrrolo[2,1-a]isoquinoline-3-carboxylate；Ethyl 1-(3,4-dimethoxyphenyl)-2-(4,5-dimethoxy-2-phenylmethoxyphenyl)-8,9-dimethoxy-5,6-dihydropyrrolo[2,1-a]isoquinoline-3-carboxylate
• CAS: 858520-96-4
• 化学式: C₄₀H₄₁NO₉
• 分子量: 679.767
• InChiKey: MJZJMXIKVFSALD-UHFFFAOYSA-N

物化性质

• 沸点：
  778.4±60.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  50
• 可旋转键数：
  14
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  95.8
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  ethyl 1-(3,4-dimethoxyphenyl)-2-(2-benzyloxy-4,5-dimethoxyphenyl)-8,9-dimethoxy-5,6-dihydropyrrolo[2,1-a]isoquinoline-3-carboxylate 在 palladium on activated charcoal 、 氢气 、 溶剂黄146 、 三乙胺 作用下， 以 乙醇 、 甲醇 为溶剂， 以72%的产率得到14-(3,4-dimethoxyphenyl)-2,3,11,12-tetramethoxy-8,9-dihydro-6H-chromeno[4',3':4,5]pyrrolo[2,1-a]isoquinolin-6-one
  参考文献：
  名称：

  木糖苷G三甲基醚通过烯胺酮中间体的木糖化学启发合成

  摘要：

  已经从原理上可以从木糖化学（木质生物质）来源衍生的前体和溶剂实现了简明的高收率的lamellarin G三甲基醚合成。该路线是相对绿色的，因为一些反应是在没有溶剂或相对温和的溶剂的情况下进行的。另外，避免了产物的色谱纯化，并且仅进行一次水性后处理。合成的新颖性在于用于构建中心吡咯环的烯胺酮的中间体。该产品的总产率是迄今为止报道的最高的。

  DOI：

  10.1021/acs.joc.9b01604
• 作为产物：
  描述：

  (3,4-二甲氧基苯基)乙酰氯 在 碳酸氢钠 、 sodium carbonate 、 三氯氧磷 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 23.0h， 生成 ethyl 1-(3,4-dimethoxyphenyl)-2-(2-benzyloxy-4,5-dimethoxyphenyl)-8,9-dimethoxy-5,6-dihydropyrrolo[2,1-a]isoquinoline-3-carboxylate
  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

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。
• 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.
• A Xylochemically Inspired Synthesis of Lamellarin G Trimethyl Ether via an Enaminone Intermediate
  作者：Robin Klintworth、Charles B. de Koning、Till Opatz、Joseph P. Michael

  DOI：10.1021/acs.joc.9b01604

  日期：2019.9.6

  A concise high yielding synthesis of lamellarin G trimethyl ether has been achieved from precursors and solvents that can in principle be derived from xylochemical (woody biomass) sources. The route is comparatively green in that some reactions are performed without solvent or with relatively benign solvents. In addition, chromatographic purification of products is avoided, and only a single aqueous

  已经从原理上可以从木糖化学（木质生物质）来源衍生的前体和溶剂实现了简明的高收率的lamellarin G三甲基醚合成。该路线是相对绿色的，因为一些反应是在没有溶剂或相对温和的溶剂的情况下进行的。另外，避免了产物的色谱纯化，并且仅进行一次水性后处理。合成的新颖性在于用于构建中心吡咯环的烯胺酮的中间体。该产品的总产率是迄今为止报道的最高的。
• 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.