1-(2,3,4,5,6-pentamethylbenzyl)-1,4-diazabicyclo[2.2.2]octan-1-ium tetrafluoroborate | 1392323-04-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(2,3,4,5,6-pentamethylbenzyl)-1,4-diazabicyclo[2.2.2]octan-1-ium tetrafluoroborate
• 英文别名: 1-[(2,3,4,5,6-Pentamethylphenyl)methyl]-4-aza-1-azoniabicyclo[2.2.2]octane;tetrafluoroborate；1-[(2,3,4,5,6-pentamethylphenyl)methyl]-4-aza-1-azoniabicyclo[2.2.2]octane;tetrafluoroborate
• CAS: 1392323-04-4
• 化学式: BF₄*C₁₈H₂₉N₂
• 分子量: 360.246
• InChiKey: QOEWCQKUHYAIAK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-(2,3,4,5,6-pentamethylbenzyl)-1,4-diazabicyclo[2.2.2]octan-1-ium tetrafluoroborate 在 silver tetrafluoroborate 、 溴 作用下， 以 乙腈 、 正己烷 、 二氯甲烷 为溶剂， 反应 0.21h， 以74%的产率得到3BF₄^(1-)*C₃₆H₅₈BrN₄⁽³⁺⁾
  参考文献：
  名称：

  Enantioselective Halocyclization Using Reagents Tailored for Chiral Anion Phase-Transfer Catalysis

  摘要：

  A chiral anion phase-transfer system for enantioselective halogenation is described. Highly insoluble, ionic reagents were developed as electrophilic bromine and iodine sources, and application of this system to o-anilidostyrenes afforded halogenated 4H-3,1-benzoxazines with excellent yield and enantioselectivity.

  DOI：

  10.1021/ja305795x
• 作为产物：
  描述：

  2,3,4,5,6-五甲基苄氯 以 乙醚 、 乙腈 为溶剂， 生成 1-(2,3,4,5,6-pentamethylbenzyl)-1,4-diazabicyclo[2.2.2]octan-1-ium tetrafluoroborate
  参考文献：
  名称：

  布朗斯台德酸与相转移催化在 Enesultam 的对映选择性跨环氨基卤化反应中的比较

  摘要：

  立体控制：我们利用手性布朗斯台德酸和相转移催化研究了不饱和中型环状苯并磺酰胺的对映选择性跨环氨基卤化。还利用计算工具研究了反应机理；我们观察到立体控制的关键步骤涉及九元环状起始材料的相互转换平面手性构象异构体的参与

  DOI：

  10.1002/chem.202202267

文献信息

• [EN] ASYMMETRIC ELECTROPHILIC FLUORINATION USING AN ANIONIC CHIRAL PHASE-TRANSFER CATALYST<br/>[FR] FLUORATION ÉLECTROPHILE ASYMÉTRIQUE UTILISANT UN CATALYSEUR DE TRANSFERT DE PHASE CHIRAL ANIONIQUE
  申请人：UNIV CALIFORNIA

  公开号：WO2013096971A1

  公开（公告）日：2013-06-27

  The discovery of distinct modes of asymmetric catalysis has the potential to rapidly advance chemists' ability to build enantioenriched molecules. As an example, the use of chiral cation salts as phase-transfer catalysts for anionic reagents has enabled a vast set of enantioselective transformations. A largely overlooked analogous mechanism wherein a chiral anionic catalyst brings a cationic species into solution is itself a powerful method. The concept is broadly applicable to a number of different reaction pathways, including to the enantioselective fluorocyclization of olefins, and dearomatization of aromatic systems with a cationic electrophile-transferring (e.g., fluorinating) agent and a chiral phosphate catalyst. The reactions proceed in high yield and stereoselectivity. The compounds and methods of the invention are of particular value, especially considering the scarcity of alternative approaches.

  发现不对称催化的不同模式具有潜力快速推动化学家构建手性富集分子的能力。例如，使用手性阳离子盐作为相转移催化剂用于阴离子试剂已经实现了大量手性选择性转化。一个被大多数人忽视的类似机制是手性阴离子催化剂将阳离子物种溶解到溶液中，这本身就是一种强大的方法。这一概念广泛适用于许多不同的反应途径，包括对烯烃进行手性选择性氟环化和用阳离子亲电试剂转移（例如，氟化）剂和手性磷酸盐催化剂进行芳香系统去芳构化。这些反应产率高，立体选择性好。该发明的化合物和方法具有特殊价值，尤其考虑到替代方法的稀缺性。
• Enantioselective Halocyclization Using Reagents Tailored for Chiral Anion Phase-Transfer Catalysis
  作者：Yi-Ming Wang、Jeffrey Wu、Christina Hoong、Vivek Rauniyar、F. Dean Toste

  DOI：10.1021/ja305795x

  日期：2012.8.8

  A chiral anion phase-transfer system for enantioselective halogenation is described. Highly insoluble, ionic reagents were developed as electrophilic bromine and iodine sources, and application of this system to o-anilidostyrenes afforded halogenated 4H-3,1-benzoxazines with excellent yield and enantioselectivity.
• Brønsted Acid versus Phase‐Transfer Catalysis in the Enantioselective Transannular Aminohalogenation of Enesultams
  作者：Javier Luis‐Barrera、Sandra Rodriguez、Uxue Uria、Efraim Reyes、Liher Prieto、Luisa Carrillo、Manuel Pedrón、Tomás Tejero、Pedro Merino、Jose L. Vicario

  DOI：10.1002/chem.202202267

  日期：2022.11.7

  Stereocontrol: We have studied the enantioselective transannular aminohalogenation of unsaturated medium-sized cyclic benzosulfonamides by using both chiral Brønsted acid and phase-transfer catalysis. The mechanism of the reaction was also studied by using computational tools; we observed that the key step for stereocontrol involves the participation of an interconverting planar chiral conformer of

  立体控制：我们利用手性布朗斯台德酸和相转移催化研究了不饱和中型环状苯并磺酰胺的对映选择性跨环氨基卤化。还利用计算工具研究了反应机理；我们观察到立体控制的关键步骤涉及九元环状起始材料的相互转换平面手性构象异构体的参与