(diallyl)(6-bromobenzo[1,3]dioxol-5-ylmethyl)amine | 872831-70-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: (diallyl)(6-bromobenzo[1,3]dioxol-5-ylmethyl)amine
• 英文别名: 6-bromo-N,N-diallylpiperonylamine；N-[(6-bromo-1,3-benzodioxol-5-yl)methyl]-N-prop-2-enylprop-2-en-1-amine
• CAS: 872831-70-4
• 化学式: C₁₄H₁₆BrNO₂
• 分子量: 310.191
• InChiKey: GDRYLADPACXXRR-UHFFFAOYSA-N

物化性质

• 沸点：
  348.4±42.0 °C(Predicted)
• 密度：
  1.351±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (diallyl)(6-bromobenzo[1,3]dioxol-5-ylmethyl)amine 在 正丁基锂 、 叔丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 1.0h， 生成 (diallyl)[6-(2-methoxyvinyl)benzo[1,3]dioxol-5-ylmethyl]amine
  参考文献：
  名称：

  Asymmetric Total Synthesis of the 1-epi-Aglycon of the Cripowellins A and B

  摘要：

  [GRAPHICS]The unusual [5.3.2]-bicyclic structure of the insecticidal Amaryllidaceae alkaloids cripowellin A (1) and B (2) has been synthesized for the first time via a sequence of Sharpless dihydroxylation, ring-closing metathesis, and intramolecular Heck reaction. The asymmetric synthesis of the 1-epiaglycon 82 proceeds with virtually complete diastereo- and enantioselectivity (de, ee >= 98%) in 13 steps and an overall yield of 5.6%. In addition, three alternative approaches toward the aglycon 3 are also described focusing on (1) the alkylation of the 2-benzazepinedithianes 35 and 36 with the electrophile 11, (2) a radical cyclization of the precursor (R/S,S,S)-39, and (3) an intramolecular arylation reaction of the aryl ketone 47.

  DOI：

  10.1021/jo0518093
• 作为产物：
  描述：

  3-溴丙烯 、 (6-溴-苯并[D][1,3]二氧杂环戊烯-5-基)甲胺 在 N,N-二异丙基乙胺 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以85%的产率得到(diallyl)(6-bromobenzo[1,3]dioxol-5-ylmethyl)amine
  参考文献：
  名称：

  Asymmetric Total Synthesis of the 1-epi-Aglycon of the Cripowellins A and B

  摘要：

  [GRAPHICS]The unusual [5.3.2]-bicyclic structure of the insecticidal Amaryllidaceae alkaloids cripowellin A (1) and B (2) has been synthesized for the first time via a sequence of Sharpless dihydroxylation, ring-closing metathesis, and intramolecular Heck reaction. The asymmetric synthesis of the 1-epiaglycon 82 proceeds with virtually complete diastereo- and enantioselectivity (de, ee >= 98%) in 13 steps and an overall yield of 5.6%. In addition, three alternative approaches toward the aglycon 3 are also described focusing on (1) the alkylation of the 2-benzazepinedithianes 35 and 36 with the electrophile 11, (2) a radical cyclization of the precursor (R/S,S,S)-39, and (3) an intramolecular arylation reaction of the aryl ketone 47.

  DOI：

  10.1021/jo0518093

文献信息

• Synthetic Studies for the 1,3-Iterative Organoiron Approach to the Synthesis of Siculinine: Efficient Arylation Using a Diarylcuprate Reagent
  作者：G. Richard Stephenson、Ian M. Palotai、Sarah Thomas、Michael Tinkl

  DOI：10.1002/ejoc.201201056

  日期：2013.4

  Disubstituted (cyclohexadienyl)iron(1+) complex 2b is prepared by an improved route that starts from 1,2-dimethoxycyclohexa-1,4-diene 3. In five steps, the synthesis of 2b is achieved by complexation with Fe(CO)5, hydride abstraction, hydrolysis, addition of EtO2CCH2ZrBr, and reaction with HBF4. In the presence of dimethyl sulfide, the reaction of 2b with 2-[CH2N(CH2CH=CH2)2]-functionalized diarylcuprate

  双取代（环己二烯基）铁（1+）配合物 2b 是通过改进的路线制备的，该路线从 1,2-二甲氧基环己-1,4-二烯 3 开始。 分五步，通过与 Fe(CO) 络合来合成 2b 5、氢化物提取，水解，加入EtO2C ZrBr，与HBF4反应。在二甲硫醚存在下，2b 与 2-[ N( CH=CH2)2]-官能化的二芳基铜酸盐试剂 7 反应得到 5α-芳基环己二烯配合物 1b，产率为 88%。一项 DFT 研究比较了含有螯合 NMe2 取代基的二芳基锌和二芳基铜酸盐试剂。