4-methoxy-N,N,2,6-tetramethylaniline | 82222-99-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-methoxy-N,N,2,6-tetramethylaniline
• CAS: 82222-99-9
• 化学式: C₁₁H₁₇NO
• 分子量: 179.262
• InChiKey: SSJJXGZKZZUROB-UHFFFAOYSA-N

物化性质

• 沸点：
  266.4±28.0 °C(Predicted)
• 密度：
  0.974±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-methoxy-N,N,2,6-tetramethylaniline 在 亚硝酸 硝酸 作用下， 反应 1.0h， 生成 2,6-二甲基-2,5-环己二烯-1,4-二酮
  参考文献：
  名称：

  Helsby, Paul; Ridd, John H., Journal of the Chemical Society. Perkin transactions II, 1983, p. 311 - 316

  摘要：

  DOI：
• 作为产物：
  描述：

  tert-butyl (4-hydroxy-2,6-dimethylphenyl)carbamate 在 正丁基锂 、 sodium hydride 、 potassium carbonate 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 、 mineral oil 为溶剂， 反应 15.34h， 生成 4-methoxy-N,N,2,6-tetramethylaniline
  参考文献：
  名称：

  B(C₆F₅)₃-Catalyzed C–H Alkylation of N-Alkylamines Using Silicon Enolates without External Oxidant

  摘要：

  An efficient method for the coupling of N-alkylamines with silicon enolates to generate beta-amino carbonyl compounds is disclosed. These reactions proceed by activation of alpha-amino C-H bonds by B(C6F5)(3), which likely generates a "frustrated" acid/base complex in the presence of large N-alkylamines. The transformation requires no external oxidant and releases hydrosilane as a byproduct. The utility of this method is demonstrated in the late-stage functionalization of bioactive molecules such as citalopram, atomoxetine, and fluoxetine.

  DOI：

  10.1021/acs.orglett.8b03959

文献信息

• Direct Conversion of <i>N</i>-Alkylamines to <i>N</i>-Propargylamines through C–H Activation Promoted by Lewis Acid/Organocopper Catalysis: Application to Late-Stage Functionalization of Bioactive Molecules
  作者：Jessica Z. Chan、Ahmet Yesilcimen、Min Cao、Yuyang Zhang、Bochao Zhang、Masayuki Wasa

  DOI：10.1021/jacs.0c08599

  日期：2020.9.23

  In the past, such transformations were carried out under oxidative conditions, and the enantioselective variants were confined to tetrahydroisoquinoline derivatives. Here, we disclose a method for union of N-alkylamines and trimethylsilyl alkynes, without the presence of an external oxidant, and promoted through cooperative actions of two Lewis acids, B(C6F5)3 and a Cu-based complex. A variety of propargylamines

  开发了一种将 N-烷基胺的 α-CH 键转化为 α-C-炔基键的有效催化方法。过去，这种转化是在氧化条件下进行的，对映选择性变体仅限于四氢异喹啉衍生物。在这里，我们公开了一种在不存在外部氧化剂的情况下结合 N-烷基胺和三甲基甲硅烷基炔的方法，并通过两种路易斯酸 B(C6F5)3 和 Cu 基络合物的协同作用进行促进。可以高非对映选择性和对映选择性合成多种炔丙胺。生物活性胺的后期位点选择性修饰证明了该方法的实用性。介绍了阐明催化过程的各种机制细微差别的动力学研究。
• C–H Functionalization of Amines via Alkene-Derived Nucleophiles through Cooperative Action of Chiral and Achiral Lewis Acid Catalysts: Applications in Enantioselective Synthesis
  作者：Ming Shang、Jessica Z. Chan、Min Cao、Yejin Chang、Qifan Wang、Brennan Cook、Sebastian Torker、Masayuki Wasa

  DOI：10.1021/jacs.8b06699

  日期：2018.8.22

  N-alkylamines and α,β-unsaturated compounds, performed under redox-neutral conditions, and promoted through concerted action of seemingly competitive Lewis acids, B(C6F5)3, and a chiral Mg-PyBOX complex. Thus, a wide variety of β-amino carbonyl compounds may be synthesized, with complete atom economy, through stereoselective reaction of an in situ-generated enantiomerically enriched Mg-enolate and an appropriate

  已经开发了 α-氨基 CH 键的催化转化，以提供有价值的对映体富集的 α-取代胺，这些实体在药物和生物活性天然产品中很普遍。通常，此类过程在氧化条件下进行并且需要贵金属基催化剂。在这里，我们公开了 N-烷基胺和 α,β-不饱和化合物的对映选择性结合的策略，在氧化还原中性条件下进行，并通过看似有竞争力的路易斯酸、B(C6F5)3 和手性镁的协同作用促进-PyBOX 复合体。因此，通过原位生成的对映体富集的镁烯醇化物和合适的亲电子试剂的立体选择性反应，可以合成多种 β-氨基羰基化合物，具有完全的原子经济性。
• Borane/Gold(I)‐Catalyzed C−H Functionalization Reactions and Cycloaddition Reactions of Amines and α‐Alkynylenones
  作者：Jun‐Jie Tian、Wei Sun、Rui‐Rui Li、Gui‐Xiu Tian、Xiao‐Chen Wang

  DOI：10.1002/anie.202208427

  日期：2022.8.26

  generated in situ from α-alkynylenones and gold catalysts were successfully used for borane-catalyzed amine C−H functionalization reactions, giving amine derivatives bearing a furan ring. The reactions took place either via an α-furylation pathway or via a [3+2] cycloaddition pathway, depending on the alkyl groups attached to the amine.

  由 α-亚炔酮和金催化剂原位生成的金-呋喃基 1,3-偶极子成功地用于硼烷催化的胺 C-H 官能化反应，得到带有呋喃环的胺衍生物。该反应通过α-呋喃化途径或通过[3+2]环加成途径发生，这取决于与胺连接的烷基。
• B(C₆F₅)₃-Catalyzed C–H Alkylation of <i>N</i>-Alkylamines Using Silicon Enolates without External Oxidant
  作者：Jessica Z. Chan、Yejin Chang、Masayuki Wasa

  DOI：10.1021/acs.orglett.8b03959

  日期：2019.2.15

  An efficient method for the coupling of N-alkylamines with silicon enolates to generate beta-amino carbonyl compounds is disclosed. These reactions proceed by activation of alpha-amino C-H bonds by B(C6F5)(3), which likely generates a "frustrated" acid/base complex in the presence of large N-alkylamines. The transformation requires no external oxidant and releases hydrosilane as a byproduct. The utility of this method is demonstrated in the late-stage functionalization of bioactive molecules such as citalopram, atomoxetine, and fluoxetine.
• Helsby, Paul; Ridd, John H., Journal of the Chemical Society. Perkin transactions II, 1983, p. 311 - 316
  作者：Helsby, Paul、Ridd, John H.

  DOI：——

  日期：——