6-[2-(2-bromo-5-methoxyphenyl)ethyl]-1,4-dioxaspiro[4,5]decane-7-carboxaldehyde | 455330-75-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 6-[2-(2-bromo-5-methoxyphenyl)ethyl]-1,4-dioxaspiro[4,5]decane-7-carboxaldehyde
• 英文别名: 6-[2-(2-Bromo-5-methoxyphenyl)ethyl]-1,4-dioxaspiro[4.5]decane-7-carbaldehyde
• CAS: 455330-75-3
• 化学式: C₁₈H₂₃BrO₄
• 分子量: 383.282
• InChiKey: FRPATRGMDGYXJX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6-[2-(2-bromo-5-methoxyphenyl)ethyl]-1,4-dioxaspiro[4,5]decane-7-carboxaldehyde 在 bis-triphenylphosphine-palladium(II) chloride caesium carbonate 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 60.0h， 以71%的产率得到7'-Methoxyspiro[1,3-dioxolane-2,1'-2,3,4,9,10,10a-hexahydrophenanthrene]-4'a-carbaldehyde
  参考文献：
  名称：

  壳素型附子生物碱的合成研究。第1部分：含有C14–C20键的四环中间体的制备

  摘要：

  分三部分介绍了（±）-代胺（一种hetisine型附子生物碱）的总合成的全部详细信息。在这里（第1部分），我们描述了关键的四环中间体6的制备。我们的钯催化的分子内α-芳基化被用于制备具有角甲酰基的中间体4。然后缩醛-烯反应物采用C14-C20键形成，以确保6从5。讨论了乙缩醛反应的反应机理，并开发了一种从6中除去2-羟乙基的方法。

  DOI：

  10.1016/j.tet.2006.04.084
• 作为产物：
  描述：

  6-[2-(2-bromo-5-methoxyphenyl)ethyl]-7-(nitromethyl)-1,4-dioxaspiro[4,5]decane 在 氢氧化钾 、 potassium permanganate 、 magnesium sulfate 作用下， 以 甲醇 、 水 为溶剂， 以75%的产率得到6-[2-(2-bromo-5-methoxyphenyl)ethyl]-1,4-dioxaspiro[4,5]decane-7-carboxaldehyde
  参考文献：
  名称：

  Synthesis of a compound having the essential structural unit for the hetisine-type of aconite alkaloids

  摘要：

  A hexacyclic compound 1, which carries an almost full structure of the hetisine skeleton lacking only the six-membered ring with an exo methylene group. was synthesized by applying an acetal-ene reaction on 5 for the bond formation of C-14 and C-20 as well as stereoselective hydrocyanation reaction on 7 for construction of the azabicyclo ring system. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00453-7

文献信息

• Palladium-catalyzed intramolecular α-arylation of aliphatic ketone, formyl, and nitro groups
  作者：Hideaki Muratake、Mitsutaka Natsume、Hiroshi Nakai

  DOI：10.1016/j.tet.2004.09.112

  日期：2004.12

  Intramolecular arylation of properly designed substrates bearing a ketone, formyl, or nitro terminating group was achieved by use of a PdCl2(Ph3P)2–Cs2CO3 reaction system to form a variety of carbocyclic compounds. Arylation in ketone compounds afforded benzene-annulated bridged or spirocycloalkanone derivatives, depending on the structure of the cyclization precursors. Arylation in formyl compounds

  通过使用PdCl 2（Ph 3 P）2 -Cs 2 CO 3，对设计适当的带有酮，甲酰基或硝基终止基团的底物进行分子内芳构化反应体系形成各种碳环化合物。取决于环化前体的结构，酮化合物中的芳基化可提供苯环化的桥环或螺环烷酮衍生物。取决于环化前体的结构和反应溶剂，甲酰基化合物中的芳基化发生在α位置（α-芳基化）或羰基碳（羰基芳基化）。α-芳基化的仲硝基以Nef反应的方式部分转化为酮，而叔硝基被部分消除，得到苯乙烯型烯烃。
• Intramolecular cyclization using palladium-catalyzed arylation toward formyl and nitro groups
  作者：Hideaki Muratake、Hiroshi Nakai

  DOI：10.1016/s0040-4039(99)00185-9

  日期：1999.3

  Intramolecular arylation of properly designed substrates bearing a formyl or nitro terminating group was achieved employing a PdCl2(Ph3P)(2)-Cs2CO3 catalyst system to form various carbocyclic compounds. Arylation toward the formyl group occurred at the a-position (alpha-arylation) or at the carbonyl carbon (carbonyl-arylation) depending on the structure of the substrates and on the reaction solvent. The cl-arylated secondary nitro group was partially transformed to ketone, whereas the tertiary nitro group was partially eliminated to a styrene type of olefin. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthetic study of hetisine-type aconite alkaloids. Part 1: Preparation of tetracyclic intermediate containing the C14–C20 bond
  作者：Hideaki Muratake、Mitsutaka Natsume

  DOI：10.1016/j.tet.2006.04.084

  日期：2006.7

  Full details for the total synthesis of (±)-nominine, a hetisine-type aconite alkaloid, are presented in three parts. Here (part 1), we describe the preparation of the key tetracyclic intermediate 6. Our palladium-catalyzed intramolecular α-arylation was adopted for preparation of the intermediate 4 with an angular formyl group. An acetal–ene reaction was then employed for C14–C20 bond formation to

  分三部分介绍了（±）-代胺（一种hetisine型附子生物碱）的总合成的全部详细信息。在这里（第1部分），我们描述了关键的四环中间体6的制备。我们的钯催化的分子内α-芳基化被用于制备具有角甲酰基的中间体4。然后缩醛-烯反应物采用C14-C20键形成，以确保6从5。讨论了乙缩醛反应的反应机理，并开发了一种从6中除去2-羟乙基的方法。
• Synthesis of a compound having the essential structural unit for the hetisine-type of aconite alkaloids
  作者：Hideaki Muratake、Mitsutaka Natsume

  DOI：10.1016/s0040-4039(02)00453-7

  日期：2002.4

  A hexacyclic compound 1, which carries an almost full structure of the hetisine skeleton lacking only the six-membered ring with an exo methylene group. was synthesized by applying an acetal-ene reaction on 5 for the bond formation of C-14 and C-20 as well as stereoselective hydrocyanation reaction on 7 for construction of the azabicyclo ring system. (C) 2002 Elsevier Science Ltd. All rights reserved.