(E)-1-(p-tolyl)-2-(trimethylsilyl)diazene

• 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: (E)-1-(p-tolyl)-2-(trimethylsilyl)diazene
• 化学式: C₁₀H₁₆N₂Si
• 分子量: 192.336
• InChiKey: JLBZJNZBGGYLIK-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  24.72
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (E)-1-(p-tolyl)-2-(trimethylsilyl)diazene 在 cesium fluoride 作用下， 以 N,N-二甲基甲酰胺-d7 为溶剂， 反应 1.0h， 以18%的产率得到对甲苯三甲基硅烷
  参考文献：
  名称：

  多氟芳烃和功能化、掩蔽的芳基亲核试剂的无过渡金属偶联

  摘要：

  报道了足够缺电子的氟化芳烃和官能化的N-芳基-N'-甲硅烷基二氮烯作为掩蔽的芳基亲核试剂的化学选择性 C(sp 2 )-C(sp 2 ) 偶联。氟化物促进的转化涉及原位生成用各种敏感官能团修饰的芳基亲核试剂，然后逐步进行亲核芳族取代 (S N Ar)。这些反应通常在室温下在几分钟内进行。这种催化过程允许两个偶联伙伴的功能化，以良好的产率提供高度氟化的联芳基化合物。

  DOI：

  10.1002/chem.202101731
• 作为产物：
  描述：

  4-甲基苯肼盐酸盐 在 偶氮二甲酸二叔丁酯 、 三乙胺 作用下， 以 乙醚 、 正戊烷 为溶剂， 反应 15.5h， 生成 (E)-1-(p-tolyl)-2-(trimethylsilyl)diazene
  参考文献：
  名称：

  General Synthesis and Optical Properties of N-Aryl-N′-Silyldiazenes

  摘要：

  While organo-substituted diazenes (R-1-N=N-R-2 with R = alkyl, aryl) are a well-studied class, of compounds, much less is known about their heavier group 14 analogues, notably because of their perceived instability. We report herein a general oxidative protocol to prepare various N-aryl-N'-silyldiazenes by a fast and mild dehydrogenation of the corresponding silylhydrazines using di-tert-butylazodicar-boxylate as an oxidant. The optical properties of these stable blue to purple silyldiazenes were also studied by UV/visible absorption spectroscopy and supported by TD-DFT calculations.

  DOI：

  10.1021/acs.organomet.9b00654

文献信息

• Synthesis of Non‐Symmetric Azoarenes by Palladium‐Catalyzed Cross‐Coupling of Silicon‐Masked Diazenyl Anions and (Hetero)Aryl Halides
  作者：Lucie Finck、Martin Oestreich

  DOI：10.1002/anie.202210907

  日期：2022.10.4

  non-symmetric azobenzene derivatives by an unprecedented C(sp2)−N(sp2) cross-coupling is presented. N-Aryl-N′-silyldiazenes are employed as diazenyl anion equivalents that can be selectively coupled under palladium catalysis with a large array of (hetero)aryl bromides in high yields. The functional-group tolerance on either (hetero)aryl ring is excellent.

  提出了通过前所未有的 C(sp 2 )−N(sp 2 ) 交叉偶联合成非对称偶氮苯衍生物的一般策略。 N-芳基-N'-甲硅烷基二氮烯用作二氮烯基阴离子等价物，可以在钯催化下选择性地与大量（杂）芳基溴以高产率偶联。任一（杂）芳环上的官能团耐受性都非常出色。
• Fluoride-Catalyzed Arylation of α-(Trifluoromethyl)styrene Derivatives with Silicon-Masked, Functionalized Aryl Pronucleophiles
  作者：Aliyaah J. M. Rahman、Yannan Xu、Martin Oestreich

  DOI：10.1021/acs.orglett.3c02021

  日期：2023.8.4

  arylation of α-(trifluoromethyl)styrene derivatives with silicon-protected functionalized aryl pronucleophiles is disclosed. Catalytic amounts of an anionic Lewis base such as fluoride trigger the release of the aryl nucleophile from N-aryl-N′-silyldiazenes by desilylation along with denitrogenation. The thus-generated carbon nucleophiles engage in an allylic displacement with α-(trifluoromethyl)styrene electrophiles

  公开了一种操作简单的无过渡金属方案，用于用硅保护的官能化芳基亲核试剂对α-(三氟甲基)苯乙烯衍生物进行芳基化。催化量的阴离子路易斯碱（例如氟化物）通过脱甲硅烷基化和脱氮，触发芳基亲核试剂从N-芳基-N'-甲硅烷基二氮烯中释放。由此产生的碳亲核试剂与α-(三氟甲基)苯乙烯亲电子试剂发生烯丙基置换，得到相应的偕二氟烯烃。
• Palladium-Catalyzed Denitrogenative Cross-Coupling of Silicon-Masked, Aryl-Substituted Diazenes and Aryl Bromides
  作者：Lucie Finck、Sarah Dabrowski、Martin Oestreich

  DOI：10.1055/a-1988-6052

  日期：——

  A denitrogenative palladium-catalyzed C(sp2)–C(sp2) cross-coupling of aryl-substituted diazenes capped with a trimethylsilyl group and functionalized aryl bromides is reported. A PEPPSI™ catalyst in the presence of NaOt-Bu enables the activation of the N-aryl-N′-silyldiazene pronucleophile with concomitant loss of dinitrogen and subsequent coupling of the in-situ-formed aryl nucleophile. By this, biaryl

  报道了一种脱氮钯催化的 C(sp 2 )–C(sp 2 ) 交叉偶联，芳基取代的二氮烯被三甲基甲硅烷基和功能化的芳基溴化物封端。存在 NaO t -Bu 的PEPPSI ™ 催化剂能够激活N -芳基 - N '-甲硅烷基二氮烯亲核试剂，同时失去二氮并随后偶联原位形成的芳基亲核试剂。由此，可以制备带有各种取代基的联芳基化合物。
• Synthesis of Benzhydryl-Substituted Amines by Silanolate-Mediated Aldimine Arylation with Functionalized Aryl Nucleophiles Released from Diazene-Based Reagents
  作者：Aliyaah J. M. Rahman、Lucie Finck、Wolfgang Obermayer、Martin Oestreich

  DOI：10.1021/acs.orglett.2c03798

  日期：2022.12.16

  imine derivatives with functionalized aryl pronucleophiles is reported. The aryl nucleophiles are released from silicon-protected aryl-substituted diazenes by desilylation with potassium trimethylsilanolate concomitant with the loss of dinitrogen. A broad range of functional groups is tolerated in the aryl nucleophile but, depending upon their electronic effect, require specific groups at the imine

  报道了一种无过渡金属的方案，用于N -苯基 - 和N -苯甲酰基取代的苯甲醛衍生亚胺衍生物与功能化芳基亲核试剂的芳基化。芳基亲核试剂通过用三甲基硅烷醇钾进行脱甲硅烷基化并伴随二氮的损失从硅保护的芳基取代的二氮烯中释放出来。芳基亲核试剂可容许多种官能团，但根据它们的电子效应，亚胺氮原子上需要特定的基团。
• General Synthesis and Optical Properties of <i>N</i>-Aryl-<i>N</i>′-Silyldiazenes
  作者：Clément Chauvier、Lucie Finck、Stefan Hecht、Martin Oestreich

  DOI：10.1021/acs.organomet.9b00654

  日期：2019.12.23

  While organo-substituted diazenes (R-1-N=N-R-2 with R = alkyl, aryl) are a well-studied class, of compounds, much less is known about their heavier group 14 analogues, notably because of their perceived instability. We report herein a general oxidative protocol to prepare various N-aryl-N'-silyldiazenes by a fast and mild dehydrogenation of the corresponding silylhydrazines using di-tert-butylazodicar-boxylate as an oxidant. The optical properties of these stable blue to purple silyldiazenes were also studied by UV/visible absorption spectroscopy and supported by TD-DFT calculations.