4-methoxy-N-tritylaniline

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 4-methoxy-N-tritylaniline
• 英文别名: N-trityl-4-methoxyaniline；N-trityl-p-anisidine；N-Trityl-p-anisidin
• 化学式: C₂₆H₂₃NO
• 分子量: 365.475
• InChiKey: UMGKRKYAKGKIIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-methoxy-N-tritylaniline 在 四氢呋喃 、 titanium(III) chloride 、 lithium 作用下， 反应 2.0h， 以65%的产率得到甲氧苯胺
  参考文献：
  名称：

  LOW-VALENT TITANIUM MEDIATED REDUCTIVE CLEAVAGE OFO/N-TRITYL BONDS VIA FREE RADICAL PATHWAY

  摘要：

  Low-valent titanium mediated cleavage of trityl-O/N bonds in trityl ethers/amines via electron transfer process is reported. Chemoselective deprotection of trityl ethers in preference to benzyl ethers is achieved. The ease of cleavage of protected alcohols and amines is in the order O-allyl > O-trityl > O-benzyl; N-trityl > O-trityl bonds.

  DOI：

  10.1081/scc-120014795
• 作为产物：
  描述：

  三苯基甲醇 、 甲氧苯胺 在 三(五氟苯基)硼烷 作用下， 以 甲苯 为溶剂， 反应 36.0h， 以52%的产率得到4-methoxy-N-tritylaniline
  参考文献：
  名称：

  硼催化的芳胺和芳酰胺与苄醇的N-烷基化反应。

  摘要：

  提出了一种可持续的基于硼的催化方法，用于伯，仲和叔苄醇对伯和仲芳族胺和酰胺的化学选择性N-烷基化。不含金属的方案在低催化剂负载下运行，可耐受多个官能团，并生成H2O作为唯一的副产物。进行了初步的机理研究，以证明硼催化剂在中间体二苄基醚的活化中的关键作用，并确定了决定速率的步骤。

  DOI：

  10.1021/acs.joc.9b02816

文献信息

• Borane-Catalyzed Chemoselectivity-Controllable N-Alkylation and <i>ortho</i> C-Alkylation of Unprotected Arylamines Using Benzylic Alcohols
  作者：Shan-Shui Meng、Xiaowen Tang、Xiang Luo、Ruibo Wu、Jun-Ling Zhao、Albert S. C. Chan

  DOI：10.1021/acscatal.9b03038

  日期：2019.9.6

  efficient and highly chemoselective alkylation of unprotected arylamines using alcohols catalyzed by B(C6F5)3 has been developed. The reaction gives N-alkylated products and ortho C-alkylated products in different solvents in good chemoselectivities and yields. Control experiments and DFT calculations indicated that the borane underwent alcohol/arylamine exchange to ensure catalytic activity, and a

  已经开发出一种空前的方案，用于使用受B（C 6 F 5）3催化的醇对未保护的芳基胺进行高效且高度化学选择性的烷基化反应。该反应在不同溶剂中以良好的化学选择性和收率得到N-烷基化产物和邻C-烷基化产物。控制实验和DFT计算表明，硼烷进行了醇/芳基胺交换以确保催化活性，并提出了涉及碳正离子化的可能机理。
• Transition-Metal-Free Direct Arylation of Anilines
  作者：Tracey Pirali、Fengzhi Zhang、Anna H. Miller、Jenna L. Head、Donald McAusland、Michael F. Greaney

  DOI：10.1002/anie.201106150

  日期：2012.1.23

  Aryne arylation: A new method of direct arylation is reported for aniline substrates. The reaction uses benzyne to synthesize a variety of aminobiaryls under mild conditions (see scheme), requiring no stoichiometric metalation or transition‐metal catalysis. An ene mechanism is implicated, and conveys excellent functional group tolerance relative to metal‐mediated processes.

  芳基芳基化：据报道苯胺底物有一种直接芳基化的新方法。该反应使用苯炔在温和条件下合成各种氨基联芳基（参见方案），无需化学计量的金属化或过渡金属催化。涉及烯键机制，并相对于金属介导的过程传达了出色的官能团耐受性。
• Buttressing Effect as a Key Design Principle towards Highly Efficient Palladium/N-Heterocyclic Carbene Buchwald-Hartwig Amination Catalysts
  作者：Yin Zhang、Guy Lavigne、Noël Lugan、Vincent César

  DOI：10.1002/chem.201702859

  日期：2017.10.4

  The backbone substitution of the standard 1,3‐bis(2,6‐diisopropylphenyl)‐2H‐imidazol‐2‐ylidene (IPr) ligand by dimethylamino groups was previously shown to induce a dramatic improvement in the catalytic efficiency of the corresponding Pd–PEPPSI (pyridine‐enhanced pre‐catalyst preparation, stabilization, and initiation) pre‐catalysts in N‐arylation reactions. Herein, a thorough structure/activity study

  先前显示标准的1,3-双（2,6-二异丙基苯基）-2 H-咪唑-2-亚基（IPr）配体被二甲氨基取代的主链可显着提高相应Pd的催化效率N-芳基化反应中的–PEPPSI（吡啶增强的前催化剂的制备，稳定和引发）。在此，已经描述了用于合理化该有益效果的详尽的结构/活性研究。除了先前报道的IPr和IPr配体之外，新的IPr和IPr研究中设计并分析了分别带有一个较大的二异丙基氨基和二甲基氨基和氯取代基的组合的配体。发现主链取代的影响起源是空间性的，并且与芳烃化学中遇到的众所周知的支撑效应有关。通过开发一种高效的催化体系，用于庞大的α，α，α-三取代伯胺的芳基化反应，证明了这种方法的实用性和多功能性。根据[的PdCl（η优化系统3 -cinnamyl）（IPR ）]或[的PdCl（η 3 -cinnamyl）（IPR ）]预催化剂可在前所未有的温和条件下（催化剂负载量：0.5–2 mol％，反应温度：
• Silylaryl Halides Can Replace Triflates as Aryne Precursors
  作者：Milad Mesgar、Olafs Daugulis

  DOI：10.1021/acs.orglett.6b01952

  日期：2016.8.5

  Silylaryl bromides and iodides can be prepared in one step from commercially available starting materials. Arynes can be generated from these compounds under conditions nearly identical to those employed for silylaryl triflates. Three distinct transformations, ortho-arylation of N-tritylanilines, intermolecular addition of arynes to amides, and reaction of ureas with arynes, were shown to be successful for the new aryne precursors. The main advantage of silylaryl halides relative to silyl aryl triflates is their one-step preparation from commercially available starting materials.
• Unexpected [M]+ radical ions deriving from the cleavage of CH bond in diarylmethylamines detected by electrospray mass spectrometry
  作者：Tian Cai、Xiao-Ying Xu、Dong-Mei Fang、Hua-Yi Qi、Yan Jiang、Guo-Lin Zhang、Zhi-Jun Wu

  DOI：10.1016/j.ijms.2014.09.001

  日期：2014.11

  Two diarylmethylamines were analyzed using electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-QTOF). Anomalous [M](center dot+) ions were detected. Interestingly, although 4-phenoxyphenol derivatives may produce radical ions by oxidation, the radical ions in diarylmethylamines detection may be formed by losing an electron from C-H bond. It was found that both the electron-donating effect of 4-methoxyaniline group and conjugation effect of the two aryl groups play an important role in stabilizing the tertiary carbon radical. Tandem mass spectra further supported the proposed structure of [M](center dot+). In addition, solvent is not involved in the formation of [M](center dot+) (C) 2014 Elsevier B.V. All rights reserved.