4-(trifluoromethyl)-4-((trimethylsilyl)oxy)cyclohexa-2,5-dienone

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 4-(trifluoromethyl)-4-((trimethylsilyl)oxy)cyclohexa-2,5-dienone
• 英文别名: 4-(Trimethylsiloxy)-4-(trifluoromethyl)-2,5-cyclohexadiene-1-one；4-(trifluoromethyl)-4-trimethylsilyloxycyclohexa-2,5-dien-1-one
• 化学式: C₁₀H₁₃F₃O₂Si
• 分子量: 250.293
• InChiKey: YGSABBPQDSGSGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.83
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-(trifluoromethyl)-4-((trimethylsilyl)oxy)cyclohexa-2,5-dienone 在 indium(III) triflate 、 copper(l) iodide 、 三甲基氯硅烷 、 氧气 作用下， 以 二甲基亚砜 、 1,2-二氯乙烷 为溶剂， 反应 8.5h， 生成 5-(butylthio)-2-(trifluoromethyl)benzaldehyde
  参考文献：
  名称：

  1,3-Carbothiolation of 4-(Trifluoromethyl)-p-Quinols: A New Access to Functionalized (Trifluoromethyl)arenes

  摘要：

  A new strategy, the 1,3-carbothiolation/aromatization, for the synthesis of functionalized (trifluoromethyl)arenes has been developed that enables the regioselective introduction of two different functional groups onto an "aromatic ring" in the meta-position to each other in a single step.

  DOI：

  10.1021/ol403096g
• 作为产物：
  描述：

  (三氟甲基)三甲基硅烷 、 对苯醌 在 potassium fluoride 作用下， 以 乙腈 为溶剂， 以15 %的产率得到4-(trifluoromethyl)-4-((trimethylsilyl)oxy)cyclohexa-2,5-dienone
  参考文献：
  名称：

  使用磺酰甲基异氰化物的铜催化烯烃化 4-CF3 取代的环己二烯酮：一种静电排斥控制的区域选择性开关策略

  摘要：

  使用磺酰甲基异氰化物开发了Cu(OTf) 2催化的环己二烯酮烯化反应。环己二烯酮 4 位的CF 3部分显示出显着的静电排斥作用，通过优先 [3+2] 环加成与酮部分产生烯化产物，随后瞬时恶唑啉中间体容易裂解。当前 Cu(II) 催化的 4-CF 3取代的环己二烯酮的烯化反应表明反应二分法涉及通过静电排斥效应在 Van Leusen 1,4-加成路径上进行CF 3控制的 1,2-加成。

  DOI：

  10.1002/adsc.202201333

文献信息

• In situ generation and reactions of p-(trifluoromethyl)benzyl electrophiles: an efficient access to p-(trifluoromethyl)benzyl compounds
  作者：Jinhuan Dong、Shuang Xin、Yanqing Wang、Ling Pan、Qun Liu

  DOI：10.1039/c6cc09268c

  日期：——

  A new three-component reaction, namely condensation-anti-Michael addition-aromatization, enables the construction of benzylic compounds. This reaction can not only act as an alternative approach to regioselective Csp2-H trifluoromethylation of arenes through...

  一种新的三组分反应，即缩合-反-迈克尔加成-芳构化，使苄基化合物的构建成为可能。该反应不仅可以作为替代方法，还可以通过...进行芳烃的区域选择性Csp2-H三氟甲基化反应。
• A Ritter-Type Route to <i>N</i>-Benzylamides by Multicomponent Reaction Based on <i>p</i>-(Trifluoromethyl)-<i>p</i>-quinols
  作者：Chengjie Feng、Yifei Li、Xinyao Sheng、Ling Pan、Qun Liu

  DOI：10.1021/acs.orglett.8b02762

  日期：2018.10.19

  A novel multicomponent reaction of p-(trifluoromethyl)- p-quinolsilyl ethers, ketones, and nitriles was developed for the efficient synthesis of p-trifluoromethylated N-benzylamides. The key step of the reaction involves the formation of an unstable condensation precursor in situ generated form the condensation of p-(trifluoromethyl)- p-quinolsilyl ethers with ketones. This work provides a significant

  开发了对-（三氟甲基）-对-喹啉甲硅烷基醚，酮和腈的新型多组分反应，以有效合成对-三氟甲基化的N-苄基酰胺。该反应的关键步骤涉及形成不稳定的缩合前体，该不稳定的缩合前体是由对-（三氟甲基）-对-喹啉甲硅烷基醚与酮的缩合而原位产生的。这项工作为Ritter型反应提供了显着的扩展，并且该反应可以在温和的反应条件下进行，并且可以耐受各种腈，包括芳基和脂族腈。
• Csp³–H bond functionalization of amines<i>via</i>tunable iminium ions: divergent synthesis of trifluoromethylated arylamines
  作者：Lou Shi、Mingshan Wang、Ling Pan、Yifei Li、Qun Liu

  DOI：10.1039/c8cc04936j

  日期：——

  A series of tunable iminium ions, generated in situ by the condensation of 4-trifluoromethyl-p-quinols with cyclic amines, can lead to the divergent synthesis of trifluoromethylated arylamines in a single step via redox-neutral isomerization. The direct α- and β-functionalization of saturated amines can be achieved regioselectively under mild conditions.

  由4-三氟甲基-对苯二酚与环胺缩合原位产生的一系列可调亚胺离子可通过氧化还原中性异构化一步完成三氟甲基化芳基胺的发散合成。在温和条件下，可以选择性地实现饱和胺的直接α-和β-官能化。
• Nucleophilic Trifluoromethylation of Carbonyl Compounds and Disulfides with Trifluoromethane and Silicon-Containing Bases
  作者：Sylvie Large、Nicolas Roques、Bernard R. Langlois

  DOI：10.1021/jo000150s

  日期：2000.12.1

  Provided that DMF (or another N,N-dialkylformamide) is present in the reaction medium, at least in a catalytic amount, fluoroform trifluoromethylates efficiently carbonyl compounds, even enolizable ones, when opposed to (TMS)(2)N- M+, generated in situ from N(TMS)(3) and M+ F- or RO- Na+ When F- is used ina catalytic amount, silylated alpha-(trifluoromethyl)carbinols are-obtained: in this case, the four-component system HCF3/N(TMS)(3)/catalytic F-/catalytic DMF behaves like the Ruppert's reagent, especially as far as nonenolizable carbonyl compounds are concerned (CF3SiMe3 remains more efficient for enolizable carbonyl compounds). This process involves an adduct between DMF and -CF3 which is the true trifluoromethylating agent. In the same way, fluoroform efficiently trifluoromethylates disulfides and diselenides when deprotonated with a strong base selected from t-BuOK or N(SiMe3)(3)/Me4NF (or TBAT). t-BuOK is more adapted to the trifluoromethylation of aryl disulfides whereas N(SiMe3)(3)/F- is well suited to that of aliphatic disulfides.
• 1,3-Carbothiolation of 4-(Trifluoromethyl)-<i>p</i>-Quinols: A New Access to Functionalized (Trifluoromethyl)arenes
  作者：Xiao Liu、Ling Pan、Jinhuan Dong、Xianxiu Xu、Qian Zhang、Qun Liu

  DOI：10.1021/ol403096g

  日期：2013.12.20

  A new strategy, the 1,3-carbothiolation/aromatization, for the synthesis of functionalized (trifluoromethyl)arenes has been developed that enables the regioselective introduction of two different functional groups onto an "aromatic ring" in the meta-position to each other in a single step.