3,3-difluoro-5-methyl-4-oxa-2-oxonia-3-boranuidabicyclo[4.4.0]deca-1,5-diene | 28329-46-6

• 英文名称: 3,3-difluoro-5-methyl-4-oxa-2-oxonia-3-boranuidabicyclo[4.4.0]deca-1,5-diene
• 英文别名: 2,2-difluoro-4-methyl-5,6,7,8-tetrahydro-2H-2λ⁴,3λ³-benzo[d][1,3,2]dioxaborinine；difluoroboron complex 2-acetylcyclohexane
• CAS: 28329-46-6
• 化学式: C₈H₁₁BF₂O₂
• 分子量: 187.982
• InChiKey: PGGCIODVHHNQEC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  3,3-difluoro-5-methyl-4-oxa-2-oxonia-3-boranuidabicyclo[4.4.0]deca-1,5-diene 在 水 作用下， 以 二甲基亚砜 为溶剂， 生成 2-乙酰基环己酮
  参考文献：
  名称：

  [EN] ONE-STEP, FAST, 18F-19F ISOTOPIC EXCHANGE RADIOLABELING OF DIFLUORO-DIOXABORININS AND USE OF SUCH COMPOUNDS IN TREATMENT
  [FR] RADIOMARQUAGE PAR ÉCHANGE ISOTOPIQUE 18F-19F RAPIDE EN UNE SEULE ÉTAPE DES DIFLUORO-DIOXABORININES ET UTILISATION DE TELS COMPOSÉS À DES FINS THÉRAPEUTIQUES

  摘要：

  公开号：

  WO2019226962A3
• 作为产物：
  描述：

  2-乙酰基环己酮 在 硼酸三丁酯 、 三氟化硼乙醚 作用下， 以 乙醚 为溶剂， 以87%的产率得到3,3-difluoro-5-methyl-4-oxa-2-oxonia-3-boranuidabicyclo[4.4.0]deca-1,5-diene
  参考文献：
  名称：

  Synthesis of new chelating ligands containing two pyrazole fragments

  摘要：

  7-[吡唑-3(5)-基]-4,5,6,7-四氢-1H-吲唑和6-[吡唑-3(5)-基]-1,4,5,6-四氢环戊并[c]吡唑，两种潜在的螯合配体，是通过将2-乙酰基环己酮和2-乙酰基环戊酮的双氟硼复合物与二甲基甲酰胺二甲基乙缩醛缩合，随后用水合肼进行环化合成的。

  DOI：

  10.1007/s11172-010-0021-7

文献信息

• Regioselective Enamine Formation from Oxonia-Boranuida-Betaines and Their Application in Asymmetric Michael Reactions
  作者：Jens Christoffers、Burkard Kreidler、Sven Unger、Wolfgang Frey

  DOI：10.1002/ejoc.200300191

  日期：2003.8

  Both enamines 4 and 5 give products with quaternary stereocenters in high selectivity in copper-catalyzed asymmetric Michael reactions with methyl vinyl ketone (8). But interestingly, exo- and endocyclic enamines are complementary with respect to stereochemistry of the subsequent Michael reactions since they give stereocenters with opposite configurations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  β-二酮硼酸甜菜碱 2 很容易通过 β-二羰基化合物 1 与 BF3·OEt2 反应得到。硼酸盐 2 与 L-缬氨酸二乙酰胺 (3a) 的反应几乎只得到环外烯胺 4 作为动力学产物。相比之下，β-二酮 1 与手性助剂 3a 的直接酸催化转化产生内环烯胺 5 作为热力学产物。烯胺 4 和 5 在铜催化的与甲基乙烯基酮 (8) 的不对称迈克尔反应中均以高选择性得到具有季立构中心的产物。但有趣的是，外环和内环烯胺在后续迈克尔反应的立体化学方面是互补的，因为它们提供具有相反构型的立体中心。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Regioselective Formation of<i>endo</i>- and<i>exo</i>-Cyclic Enamines: Both Enantio­meric Products Accessible by the Same Chiral Auxiliary
  作者：Jens Christoffers、Burkard Kreidler、Heiko Oertling、Sven Unger、Wolfgang Frey

  DOI：10.1055/s-2003-37513

  日期：——

  The copper-catalyzed conversion of exo-cyclic enamines 4a-c with methyl vinyl ketone (2) yields spirocyclic products 6a-c in a sequence of Michael and aldol reaction. The application of the chiral auxiliary l-valine diethylamide results in the formation of quaternary stereocenters with high enantiomeric excess. The configuration of intermediate imine 5a is determined to be S. Thus, exo-cyclic enamines 4 yield S-configured spiroketones 6, whereas, as shown for spiroketone ent-6c, reaction of endo-cyclic enamines such as 1 generates the opposite configuration in the products applying the same auxiliary l-valine diethylamide 9.

  铜催化的外环亚胺 4a-c 与甲基乙烯基酮 (2) 的转化通过迈克尔反应和 aldol 反应顺序生成螺环产物 6a-c。应用手性辅助剂 L-缬氨酸二乙酰胺可形成具有高对映体过剩的四面体立体中心。中间体亚胺 5a 的构型被确定为 S。因此，外环亚胺 4 生成 S 配置的螺酮 6，而对于螺酮 ent-6c，内环亚胺 1 的反应则生成与产品中相反的构型，仍然使用相同的辅助剂 L-缬氨酸二乙酰胺 9。
• Generation of Quaternary Stereocenters by Asymmetric Michael Reactions: Enamine Regiochemistry as Configuration Switch
  作者：Burkard Kreidler、Angelika Baro、Wolfgang Frey、Jens Christoffers

  DOI：10.1002/chem.200401223

  日期：2005.4.22

  condensation gives endocyclic enamines 3 as the thermodynamically favored products. Activation with Lewis acid BF(3).OEt(2) affords betaines 8 as intermediate products, which can be reacted with L-valine diethylamide (2) to preferentially furnish exocyclic enamines 4 as kinetic products. Derivatives with quaternary stereocenters were accessible from both isomeric enamines by using asymmetric, copper(II)-catalyzed

  从环状β-二酮1区域选择性烯胺的形成是由活化剂的适当选择而获得：布朗斯台德酸催化的缩合给出内环烯胺3作为热力学有利的产品。用路易斯酸BF（3）.OEt（2）活化可得到甜菜碱8，作为中间产物，可将其与L-缬氨酸二乙酰胺（2）反应，优先提供作为动力学产物的环外烯胺4。通过在环境温度下使用不对称的铜（II）催化迈克尔反应，可以从两种异构烯胺中获得具有季立体中心的衍生物。两种区域异构体都使三酮7具有相同的组成，但在四级立体中心具有相反的绝对构型。因此，
• Regiospecific bromination of condensed tetralones via aryloxydifluoroborn chelates
  作者：Shelagh C. Mackay、Peter N. Preston、Stephen G. Will、John O. Morley

  DOI：10.1039/c39820000395

  日期：——

  Bromination (Br2, CCl4) of the anthracenone derivative (1b) under thermal or photochemical conditions gives the expected bromo-compound (1d) whereas photochemical bromination of the aryloxydifluoroboron complexes (2a,b) gives products (2c,d) of benzylic substitution; conversion of (2c) and (3a,b) into anthraquinone derivatives including madeirin (4) is described and extension of the regiospecific bromination

  在热或光化学条件下，蒽酮衍生物（1b）的溴化（Br 2，CCl 4）得到预期的溴化合物（1d），而芳氧基二氟硼配合物（2a，b）的光化学溴化得到苄基产物（2c，d）代换; 描述了将（2c）和（3a，b）转化为蒽醌衍生物（包括马来酸（4）），并说明了将区域特异性溴化程序扩展为双环二氟硼配合物（5a）。
• Mechanofluorochromism of NIR-emitting dyes based on difluoroboron β-carbonyl cyclic ketonate complexes
  作者：Fushuang Zhang、Lu Zhai、Siwei Feng、Wenhua Mi、Jingbo Sun、Meng Sun、Jinyu Zhao、Ran Lu

  DOI：10.1016/j.dyepig.2018.03.069

  日期：2018.9

  New difluoroboron beta-carbonyl cyclic ketonate complexes CnB (n = 2, 16), in which carbazole was linked to difluoroboron beta-diketonate directly, and DCnB (n = 2, 16), where two terminal carbazole units were bridged by vinyl groups to link to difluoroboron beta-diketonate core, were synthesized. They exhibited reversible mechanofluorochromic (MFC) behavior under grinding/fuming or heating treatment. Particularly, the emission of DC2B and DC16B emerged in the range of 650-850 nm in the solid-state. They gave red and rose-red luminescence in the as-synthesized crystals and in the ground powders, respectively, during MFC processes. Such MFC materials emitting NIR (near-infrared) light were seldom reported. In addition, compared with C2B, CI6B showed high-contrast mechanofluorochromism because the long alkyl chain might decrease the strength of pi-pi interactions in the as-synthesized crystals, leading to the emission appeared at the high-energy region (483 nm). The disassembling of parts of pi-aggregates and the improvement of the molecular planarity led to red-shift of the emission (509 nm) upon grinding.