2-烯丙基-4-氟苯胺 | 267002-55-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-烯丙基-4-氟苯胺
• 中文别名: 吡啶,2-氯-3-(1H-咪唑-5-基)-
• 英文名称: 2-allyl-4-fluorophenylamine
• 英文别名: 2-allyl-4-fluoroaniline；2-allyl-4-flouroaniline；2-allyl-4-fluorobenzeneamine；4-fluoro-2-allylaniline；4-fluoro-2-prop-2-enylaniline
• CAS: 267002-55-1
• 化学式: C₉H₁₀FN
• 分子量: 151.184
• InChiKey: IEBPSSNXCKFXTJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-烯丙基-4-氟苯胺 在 silver tetrafluoroborate 、 C₃₆H₂₆I₂N₄Pt 、 氧气 作用下， 以 苯 为溶剂， 反应 72.0h， 以52%的产率得到5-氟-2-甲基吲哚
  参考文献：
  名称：

  A N-heterocyclic carbene (NHC) platinum complex as pre-catalyst for the intramolecular hydroamination of olefins with secondary alkylamines and oxidative amination of ω-alkenic amines

  摘要：

  A N-heterocyclic carbene (NHC) platinum complex 3 prepared from BINAM was found to be a highly effective pre-catalyst for the intramolecular hydroamination of olefins with secondary alkylamines to give the corresponding intramolecular hydroamination products in excellent yields. The substrate scope has been carefully examined and the plausible reaction mechanism has been also proposed. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.02.060
• 作为产物：
  描述：

  4-fluoro-1-nitro-2-(2-propen-1-yl)benzene 在 溶剂黄146 、 锌 作用下， 以 乙醇 为溶剂， 反应 1.0h， 生成 2-烯丙基-4-氟苯胺
  参考文献：
  名称：

  Highly Stereoselective 7-Endo-Trig/Ring Contraction Cascade To Construct Pyrrolo[1,2-a]quinoline Derivatives

  摘要：

  With the cooperation of Cram's phenonium ion, a novel cascade reaction was illustrated to construct pyrrolo[1,2-a]quinolines as a sole diastereoisomer in good to excellent yields. Preliminary mechanistic studies revealed that the gamma-lactam ring and electron-rich arene are important driving forces for ring contraction.

  DOI：

  10.1021/ol100220c

文献信息

• Pd-Catalyzed Intramolecular Aminoalkylation of Unactivated Alkenes: Access to Diverse <i>N</i>-Heterocycles
  作者：Liu Ye、Kai-Yip Lo、Qiangshuai Gu、Dan Yang

  DOI：10.1021/acs.orglett.6b03295

  日期：2017.1.20

  A highly efficient palladium-catalyzed intramolecular aminoalkylation of unactivated alkenes in the absence of an external ligand and oxidant is described. New C–N and C(sp3)–C(sp3) bonds are formed simultaneously. This general transformation allows for construction of diverse N-heterocycles. Mechanistic studies show that the process may involve a four-membered Pd(alkyl)amido intermediate.

  描述了在不存在外部配体和氧化剂的情况下未活化的烯烃的高效钯催化的分子内氨基烷基化。同时形成新的C–N和C（sp 3）–C（sp 3）键。这种一般的转变允许构建不同的N-杂环。机理研究表明，该过程可能涉及四元Pd（烷基）酰胺基中间体。
• Palladium-Catalyzed Highly Diastereoselective Oxidative Cascade Cyclization Reactions
  作者：Kai-Tai Yip、Nian-Yong Zhu、Dan Yang

  DOI：10.1021/ol900355h

  日期：2009.5.7

  Isoquinoline and quinoline have been discovered as novel ligands for palladium-catalyzed oxidative cascade cyclization reactions. With our new catalyst systems (Pd(OAc)2/isoquinoline or quinoline), unsaturated anilides cyclize under an oxygen atmosphere (1 atm) to furnish structurally versatile indoline derivatives in good yields. One C−N bond and two C−C bonds are formed in a single step with excellent

  已发现异喹啉和喹啉是钯催化的氧化级联环化反应的新型配体。借助我们的新型催化剂体系（Pd（OAc）2 /异喹啉或喹啉），不饱和酸酐在氧气气氛（1个大气压）下环化，从而以高收率提供结构多样的二氢吲哚衍生物。一步形成一个C-N键和两个C-C键，非对映选择性极好（dr> 24：1）。
• Oxidative Diamination of Alkenes with Ureas as Nitrogen Sources:  Mechanistic Pathways in the Presence of a High Oxidation State Palladium Catalyst
  作者：Kilian Muñiz、Claas H. Hövelmann、Jan Streuff

  DOI：10.1021/ja075041a

  日期：2008.1.1

  identical mechanism where stereochemistry is concerned. It exemplifies the importance of cationic palladium(IV) intermediates prior to the final reductive elimination from palladium and proves that the nucelophile for this step stems from the immediate coordination sphere of the palladium(IV) precursor. These results have important implications for the general development of alkene 1,2-difunctionalization

  最近报道了第一个钯催化的未官能化末端烯烃的分子内二胺化。本研究基于 NMR 滴定、动力学测量、竞争实验和氘标记研究了其机理过程的细节。它总结了一个两步程序，包括用未连接的钯 (II) 催化剂状态进行顺氨基钯化，然后氧化成钯 (IV)，然后形成 CN 键，得到最终产物为环状二胺。使用磺酰胺的相关反应导致烯烃的氨基烷氧基官能化。该过程使用氘代烯烃进行了研究，发现在立体化学方面遵循相同的机制。它举例说明了阳离子钯 (IV) 中间体在最终从钯中还原消除之前的重要性，并证明该步骤的亲核试剂源自钯 (IV) 前体的直接配位范围。这些结果对烯烃 1,2-双官能化的一般发展以及氨基钯化和钯催化的 C(烷基)-N 键形成的个别过程具有重要意义。
• Easy Access to Novel Tetrahydro-1-benzazepine-2-carboxylic Acids and Tetrahydro-1-benzazepines Carrying [a]-Fused Heterocyclic Units from 2-(Allylaryl)glycinates
  作者：Alirio Palma、Sergio Andrés Guerrero、Juan E. Ramírez、Carlos M. Sanabria、Lina M. Acosta、Justo Cobo、Manuel Nogueras

  DOI：10.1055/s-0040-1706484

  日期：2021.4

  Abstract A concise, efficient, and versatile approach to access novel tetrahydro-1H-benzo[b]azepine-2-carboxylic acids and tricyclic tetra­hydro-1-benzazepines carrying [a]-fused heterocyclic units is reported. The easily accessible 2-(allylaryl)glycinates were used as starting material to synthesize, via the corresponding 1,4-epoxycycloadducts, the required key intermediate benzo[b]azepine-2-carboxylates

  摘要 据报道，一种简洁，有效且通用的方法可访问带有[ a ]稠合杂环单元的新型四氢-1 H-苯并[ b ]氮杂-2-羧酸和三环四氢-1-苯并氮杂。易于获得的2-（烯丙基芳基）甘氨酸盐用作起始原料，通过相应的1，4-环氧环加合物合成所需的关键中间体苯并[ b ]氮杂-2-羧酸酯。后者的水解得到目标苯并[ b ]氮杂-2-羧酸。关键中间体也被转化为N -2-氯乙酰基衍生物，然后依次转化为相应的三环目标六氢苯并[ f ]吡嗪并[1,2-通过与苄胺或氨基乙醇反应生成]] azepine-1,4-二酮。普通中间体与肼的反应产生了相应的中间体碳酰肼，该中间体碳酰肼通过与三甲氧基甲烷反应转化为另一种三环目标四氢苯并[ f ] [1,2,4]三嗪[4,5 - a ] azepin-4（ 3 H）-一个。还报道了每种化合物的全光谱表征（IR，HRMS，1 H和13 C NMR）。 出版历史 收到：2020年7月19日
• Aerobic intramolecular aminothiocyanation of unactivated alkenes promoted by in situ generated iodine thiocyanate
  作者：Yangyang Feng、Muhammad Ijaz Hussain、Xiaohui Zhang、Jian Shi、Wen Hu、Yan Xiong

  DOI：10.1016/j.tet.2018.04.023

  日期：2018.5

  Aerobic intramolecular aminothiocyanation of unactivated alkenes has been developed by in situ generated iodine thiocyanate under open-flask conditions. This protocol provides a concise and efficient method for synthesizing SCN-containing pyrrolidine, piperidine and indoline derivatives with isolated yields of up to 87%. Furthermore, mixing iodine and sodium thiocyanate with oxygen afforded iodine

  未活化烯烃的好氧分子内氨基硫氰化反应是通过在烧瓶条件下原位生成的硫氰酸碘盐开发的。该方案为合成含SCN的吡咯烷，哌啶和二氢吲哚衍生物提供了一种简洁有效的方法，分离产率高达87％。此外，将碘和硫氰酸钠与氧气混合，得到硫氰酸碘盐（ISCN）和二硫氰酸根合碘酸盐[I（SCN）2 ] -通过液相色谱质谱法证实。机理研究表明，碘鎓离子和sulf离子中间体可能参与了这一转变。