1-(4-bromophenyl)but-3-en-1-amine

• 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-(4-bromophenyl)but-3-en-1-amine
• 化学式: C₁₀H₁₂BrN
• 分子量: 226.116
• InChiKey: QJBPQBRSRNDVJT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  吗啉 、 1-(4-bromophenyl)but-3-en-1-amine 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 1,3-双(二苯基膦)丙烷 、 silver(I) 4-methylbenzenesulfonate 作用下， 以 乙二醇二甲醚 为溶剂， 反应 48.0h， 以90%的产率得到1-(4-bromophenyl)-4-morpholinobutan-1-amine
  参考文献：
  名称：

  Anti-Markovnikov Hydroamination of Homoallylic Amines

  摘要：

  The development of an anti-Markovnikov-selective hydroamination of unactivated alkenes is a significant challenge in organometallic chemistry. Herein, we present the rhodium-catalyzed anti-Markovnikov-selective hydroamination of homoallylic amines. The proximal Lewis basic amine serves to promote reactivity and enforce regioselectivity through the formation of the favored metallacycle, thus over-riding the inherent reactivity of the alkene. The scope of both the amine nudeophiles and homoallylic amines that participate in the reaction is demonstrated.

  DOI：

  10.1021/jacs.5b08500
• 作为产物：
  描述：

  对溴苯甲醛 在 copper(II) sulfate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 26.0h， 生成 1-(4-bromophenyl)but-3-en-1-amine
  参考文献：
  名称：

  Anti-Markovnikov Hydroamination of Homoallylic Amines

  摘要：

  The development of an anti-Markovnikov-selective hydroamination of unactivated alkenes is a significant challenge in organometallic chemistry. Herein, we present the rhodium-catalyzed anti-Markovnikov-selective hydroamination of homoallylic amines. The proximal Lewis basic amine serves to promote reactivity and enforce regioselectivity through the formation of the favored metallacycle, thus over-riding the inherent reactivity of the alkene. The scope of both the amine nudeophiles and homoallylic amines that participate in the reaction is demonstrated.

  DOI：

  10.1021/jacs.5b08500

文献信息

• Controlled Reduction of Nitriles by Sodium Hydride and Zinc Chloride
  作者：Shunsuke Chiba、Derek Yiren Ong

  DOI：10.1055/s-0039-1690838

  日期：2020.5

  new protocol for the controlled reduction of nitriles to aldehydes was developed using a combination of sodium hydride and zinc chloride. The iminyl zinc intermediates derived from aromatic nitriles could be further functionalized with allylmetal nucleophiles to afford homoallylamines. As the method allows the reduction of various aliphatic and aromatic nitriles with a concise procedure under milder

  使用氢化钠和氯化锌的组合，开发了一种控制腈还原为醛的新方案。衍生自芳族腈的亚胺基锌中间体可以用烯丙基金属亲核试剂进一步官能化以提供高烯丙基胺。由于该方法可以在较温和的反应条件下以简明的方法还原各种脂族和芳族腈，并且具有广泛的官能团相容性，因此非常适合用于化学合成中的各种机会。
• α-Aminoallylation of Aldehydes with Ammonia:  Stereoselective Synthesis of Homoallylic Primary Amines
  作者：Masaharu Sugiura、Keiichi Hirano、Shū Kobayashi

  DOI：10.1021/ja049689o

  日期：2004.6.1

  Three-component reactions of aldehydes, ammonia, and allylboronates were found to provide homoallylic primary amines in high yields with high chemo- and stereoselectivities. A two-step, one-pot, stereoselective synthesis of an uncommon alpha-amino acid, alloisoleucine, was achieved utilizing this reaction.

  发现醛、氨和烯丙基硼酸酯的三组分反应以高产率和高化学和立体选择性提供均烯丙基伯胺。利用该反应实现了一种不常见的 α-氨基酸别异亮氨酸的两步、一锅、立体选择性合成。
• Formal α-Allylation of Primary Amines by a Dearomative, Palladium-Catalyzed Umpolung Allylation of <i>N</i>-(Aryloxy)imines
  作者：Luis M. Mori-Quiroz、Shrikant S. Londhe、Michael D. Clift

  DOI：10.1021/acs.joc.0c01020

  日期：2020.12.4

  N-(Aryloxy)imines, readily accessible by condensation/tautomerization of (pseudo)benzylic primary amines and 2,6-di-tert-butyl-1,4-benzoquinone, undergo efficient allylation to afford a wide range of homoallylic primary amines following hydrolytic workup. Deprotonation of N-(aryloxy)imines generates a delocalized 2-azaallyl anion-type nucleophile that engages in dearomative C–C bond-forming reactions

  N-（芳氧基）亚胺很容易通过（伪）苄基伯胺和2,6-二叔丁基-1,4-苯醌的缩合/互变异构而获得，经过有效的烯丙基化反应后得到各种均一的伯胺水解后处理。N-（芳氧基）亚胺的去质子化产生离域的2-氮杂烯丙基阴离子型亲核试剂，与烯丙基碳酸叔丁酯生成的烯丙基钯（II）亲电试剂参与脱芳香族CC键形成反应。该反应性基质使（伪）苄基伯胺的形式α-烯丙基化成为可能。机理研究表明，所需键形成事件的表观区域选择性是由非选择性烯丙基化引发的聚合过程。N-（芳氧基）亚胺产生几种区域异构体，其随后通过逐步的[1,3]-或一致的[3,3]-σ位移而重排，最终收敛以提供所需的胺产物的区域异构体。
• Acceleration effect of mild organocatalytic system 2,2′-biphenol/B(OH)3 for 2-aza-Cope rearrangement
  作者：Kenji Sugimoto、Ryoga Yoshida、Yuji Matsuya

  DOI：10.1016/j.tetlet.2022.153922

  日期：2022.7

  for 2-aza-Cope rearrangement is described. Aldehydes and 1,1-diphenyl homoallylamine were converted into the corresponding homoallylamines in moderate-to-high yield in the presence of 10 mol% 2,2′-biphenol and 30 mol% B(OH)3. In contrast to the conventional 2-aza-Cope rearrangement catalyzed by strong activators, a user- and environment-friendly organocatalytic system was established using a combination

  描述了通过结合弱酸（即 2,2'-联苯酚和 B(OH) 3）进行 2-aza-Cope 重排的有机催化作用。在 10 mol% 2,2'-联苯酚和 30 mol% B(OH) 3存在下，醛和 1,1-二苯基高烯丙胺以中等至高产率转化为相应的高烯丙胺。与由强活化剂催化的传统 2-aza-Cope 重排相比，使用廉价、易于处理、无害和工作台稳定的试剂组合建立了用户和环境友好的有机催化系统。
• Anti-Markovnikov Hydroamination of Homoallylic Amines
  作者：Seth C. Ensign、Evan P. Vanable、Gregory D. Kortman、Lee J. Weir、Kami L. Hull

  DOI：10.1021/jacs.5b08500

  日期：2015.11.4

  The development of an anti-Markovnikov-selective hydroamination of unactivated alkenes is a significant challenge in organometallic chemistry. Herein, we present the rhodium-catalyzed anti-Markovnikov-selective hydroamination of homoallylic amines. The proximal Lewis basic amine serves to promote reactivity and enforce regioselectivity through the formation of the favored metallacycle, thus over-riding the inherent reactivity of the alkene. The scope of both the amine nudeophiles and homoallylic amines that participate in the reaction is demonstrated.