5,8-difluorophthalazine | 1403599-01-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 5,8-difluorophthalazine
• CAS: 1403599-01-8
• 化学式: C₈H₄F₂N₂
• 分子量: 166.13
• InChiKey: BOXXFKOFNRGVKH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  三甲硅氧基-2-呋喃 、 5,8-difluorophthalazine 在 9,10-dimethyl-9,10-dihydro-9,10-diboraanthracene 作用下， 以 二乙二醇二甲醚 为溶剂， 反应 14.0h， 以100%的产率得到4,7-difluoro-1a,7b-dihydro-1H-cyclopropa[a]naphthalene-1-carboxylic acid
  参考文献：
  名称：

  Domino Inverse Electron-Demand Diels–Alder/Cyclopropanation Reaction of Diazines Catalyzed by a Bidentate Lewis Acid

  摘要：

  A domino inverse electron-demand Diels-Alder (IEDDA)/cyclopropanation reaction of diazines was discovered by applying electron-rich furans in the bidentate Lewis acid catalyzed IEDDA reaction. This process produces benzonorcaradienes in excellent yields with a low loading of a bidentate Lewis acid catalyst of 2 to 5 mol %. We demonstrate the broad applicability by 20 examples with different dienophiles and a variety of dienes. A detailed mechanism is proposed supported by DFT calculations.

  DOI：

  10.1021/ja308858y
• 作为产物：
  描述：

  2,5-二氟溴苯 、 N,N-二甲基甲酰胺 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正庚烷 、 乙基苯 为溶剂， 反应 1.67h， 以70%的产率得到5,8-difluorophthalazine
  参考文献：
  名称：

  Domino Inverse Electron-Demand Diels–Alder/Cyclopropanation Reaction of Diazines Catalyzed by a Bidentate Lewis Acid

  摘要：

  A domino inverse electron-demand Diels-Alder (IEDDA)/cyclopropanation reaction of diazines was discovered by applying electron-rich furans in the bidentate Lewis acid catalyzed IEDDA reaction. This process produces benzonorcaradienes in excellent yields with a low loading of a bidentate Lewis acid catalyst of 2 to 5 mol %. We demonstrate the broad applicability by 20 examples with different dienophiles and a variety of dienes. A detailed mechanism is proposed supported by DFT calculations.

  DOI：

  10.1021/ja308858y

文献信息

• Combining Bidentate Lewis Acid Catalysis and Photochemistry: Formal Insertion of <i>o</i>-Xylene into an Enamine Double Bond
  作者：Sebastian Ahles、Julia Ruhl、Marcel A. Strauss、Hermann A. Wegner

  DOI：10.1021/acs.orglett.9b01020

  日期：2019.6.7

  A bidentate Lewis acid catalyzed domino inverse-electron-demand Diels–Alder reaction combined with a photoinduced ring opening formally inserts o-xylene moieties into enamine double bonds. After reduction, phenethylamines were obtained in good yields. The scope of the reaction was determined by variation of all three starting compounds: phthalazines, aldehydes, and amines.

  双齿路易斯酸催化的多米诺骨牌逆电子需求的Diels-Alder反应与光致开环的结合将邻二甲苯基团正式插入烯胺双键中。还原后，以良好的产率获得了苯乙胺。通过改变所有三种起始化合物：酞嗪，醛和胺来确定反应范围。
• An Amine Group Transfer Reaction Driven by Aromaticity
  作者：Sebastian Ahles、Silas Götz、Luca Schweighauser、Mirko Brodsky、Simon N. Kessler、Andreas H. Heindl、Hermann A. Wegner

  DOI：10.1021/acs.orglett.8b02967

  日期：2018.11.16

  domino inverse electron-demand Diels–Alder/amine group transfer reaction catalyzed by a bidentate Lewis acid provides 1-amino-1,2-dihydronaphthalenes, a core structure in many bioactive compounds. A concerted mechanism is proposed based on experimental studies as well as DFT computations demonstrating a new general reactivity scheme. The broad scope of the reaction was evaluated by variation of all three

  双齿路易斯酸催化的立体选择性多米诺逆电子需求的Diels-Alder /胺基转移反应提供了1-氨基-1,2-二氢萘，这是许多生物活性化合物的核心结构。基于实验研究和DFT计算，提出了一种协调的机制，该机制证明了一种新的通用反应性方案。通过改变所有三种起始化合物，酞嗪，醛和胺来评估反应的广泛范围。通过克规模的反应证明了可伸缩性，而收率却没有降低。
• Synthesis of Medium-Sized Carbocycles via a Bidentate Lewis Acid-Catalyzed Inverse Electron-Demand Diels–Alder Reaction Followed by Photoinduced Ring-Opening
  作者：Julia Ruhl、Sebastian Ahles、Marcel A. Strauss、Christopher M. Leonhardt、Hermann A. Wegner

  DOI：10.1021/acs.orglett.1c00249

  日期：2021.3.19

  The combination of a Lewis acid-catalyzed inverse electron-demand Diels–Alder (IEDDA) reaction with a photoinduced ring-opening (PIRO) reaction in a domino process has been established as an efficient synthetic method to access medium-sized carbocycles. From readily available electron-rich and electron-poor phthalazines and enamines, respectively, as starting materials, various 9- and 11-membered carbocycles

  在多米诺骨牌工艺中，路易斯酸催化的逆电子需求Diels-Alder反应（IEDDA）与光致开环（PIRO）反应的结合已被确立为一种访问中型碳环化合物的有效合成方法。从容易获得的富电子和贫电子的酞嗪和烯胺分别作为起始原料，制备了各种9元和11元碳环。这种多功能的无过渡金属工具对于拓宽生物活性化合物和功能材料的结构空间将具有宝贵的价值。
• Bidentate Lewis Acid-Catalyzed Inverse Electron-Demand Diels–Alder Reaction of Phthalazines and Cyclooctynes
  作者：Hermann A. Wegner、Michel Große

  DOI：10.1055/a-2204-9522

  日期：——

  Herein we report a method for facilitating the inverse-electron-demand Diels–Alder reaction of 1,2-diazines and cyclooctynes by utilizing a boron-based bidentate Lewis acid catalyst. Readily available electron-deficient and electron-rich phthalazines proved to be suitable substrates in this transformation. The described method enables the facile construction of diversely substituted polycyclic aromatic

  在此，我们报道了一种利用硼基二齿路易斯酸催化剂促进1,2-二嗪和环辛炔的逆电子需求狄尔斯-阿尔德反应的方法。容易获得的缺电子和富电子二氮杂萘被证明是该转化中合适的底物。所述方法能够轻松构建稠合到八元碳环的不同取代的多环芳烃。