己-2-烯-1-胺 | 61210-84-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 己-2-烯-1-胺
• 英文名称: (E)-2-hexenylamin
• 英文别名: 2-hexenylamine；(E)-hex-2-en-1-amine
• CAS: 61210-84-2
• 化学式: C₆H₁₃N
• 分子量: 99.1759
• InChiKey: JMPKRWPMDAFCGM-SNAWJCMRSA-N

物化性质

• 沸点：
  140.6±9.0 °C(Predicted)
• 密度：
  0.794±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  7
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  己-2-烯-1-胺 在 二异丙胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (E)-hept-3-enenitrile
  参考文献：
  名称：

  Wolber, Erwin K. A.; Schmittel, Michael; Ruechardt, Christoph, Chemische Berichte, 1992, vol. 125, # 2, p. 525 - 532

  摘要：

  DOI：
• 作为产物：
  描述：

  (E)-2,2,2-trichloro-N-(hex-2-ene-1-yl)acetamide 在 sodium hydroxide 作用下， 反应 15.0h， 生成 己-2-烯-1-胺
  参考文献：
  名称：

  Studies of the regiospecific 3-aza-Cope rearrangement promoted by electrophilic reagents

  摘要：

  The 3-aza-Cope rearrangement of N-alkyl-N-allyl enamine substrates, which required temperatures of 250 250-degrees-C to proceed thermally, was promoted at 111-degrees-C in the presence of electrophilic reagents such as HCl (0.5 equiv) TiCl4 (0.2 equiv), AlMe3 (1.2 equiv), or (ArO)2AlMe (1.2 equiv). In order to probe the regioselectivity of this accelerated carbon-carbon bond forming process under these reaction conditions, several enamine substrates were prepared from both isobutyraldehyde and cyclohexanone. Each substrate used in these studies was prepared having an unsymmetrical N-allylic group, substituted with either an alkyl or phenyl substituent at the 4 or 6 position of the 3-aza-Cope framework. In all cam examined, reaction acceleration by the electrophilic reagent produced regiospecific [3,3] rearrangement to the corresponding products resulting from [1,3] rearrangement were not observed. Hydride reduction of the resulting imines generated the delta,epsilon-unsaturated amines in 55-94% overall yield in the three-step condensation-rearrangement-reduction process from the secondary allylamine.

  DOI：

  10.1021/jo00052a037

文献信息

• Enzymatic Primary Amination of Benzylic and Allylic C(sp³)–H Bonds
  作者：Zhi-Jun Jia、Shilong Gao、Frances H. Arnold

  DOI：10.1021/jacs.0c03428

  日期：2020.6.10

  processes are reported for their synthesis, methods that directly install a primary amine group into C(sp3)-H bonds remain unprecedented. Here, we report a set of new-to-nature enzymes that catalyzes the direct primary amination of C(sp3)-H bonds with excellent chemo-, regio-, and enantioselectivity, using a readily available hydroxylamine derivative as the nitrogen source. Directed evolution of genetically-encoded

  脂肪族伯胺普遍存在于天然产物、药物和功能材料中。虽然报道了大量合成过程，但将伯胺基团直接安装到 C(sp3)-H 键中的方法仍然是前所未有的。在这里，我们报告了一组新的天然酶，它们使用容易获得的羟胺衍生物作为氮源，以优异的化学选择性、区域选择性和对映选择性催化 C(sp3)-H 键的直接初级胺化。基因编码的细胞色素 P411 酶（P450 的血红素铁的 Cys 轴向配体已被 Ser 取代）的定向进化产生了选择性功能化苄基和烯丙基 CH 键的变体，提供了广泛的对映体富集的伯胺。
• Correction to “Rhodium/Yanphos-Catalyzed Asymmetric Interrupted Intramolecular Hydroaminomethylation of <i>trans</i>-1,2-Disubstituted Alkenes”
  作者：Caiyou Chen、Shicheng Jin、Zhefan Zhang、Biao Wei、Heng Wang、Kai Zhang、Hui Lv、Xiu-Qin Dong、Xumu Zhang

  DOI：10.1021/jacs.6b13274

  日期：2017.3.22

  mL of toluene, Rh(acac)(CO)2 as the metal precursor, (S,R)-(N-Bn)Yanphos as the ligand, CO:H2 = 10:10 bar, S/C = 20, HSiEt3 (0.3 mmol), and BF3.Et2O (0.3 mmol) The configuration of all of the products was determined to be S, except for 4m; only the desired regioisomer was obtained as determined by NMR analysis. Scheme 4. Synthetic Transformations Addition/Correction

  反应以 0.1 mmol 规模在 0.5 mL 甲苯中进行，Rh(acac)(CO)2 作为金属前体，(S,R)-(N-Bn)Yanphos 作为配体，CO:H2 = 10: 10 bar, S/C = 20, HSiEt3 (0.3 mmol), and BF3.Et2O (0.3 mmol) 通过NMR分析确定仅获得所需的区域异构体。方案 4. 合成变换加法/校正
• Rhodium/Yanphos-Catalyzed Asymmetric Interrupted Intramolecular Hydroaminomethylation of <i>trans</i>-1,2-Disubstituted Alkenes
  作者：Caiyou Chen、Shicheng Jin、Zhefan Zhang、Biao Wei、Heng Wang、Kai Zhang、Hui Lv、Xiu-Qin Dong、Xumu Zhang

  DOI：10.1021/jacs.6b03596

  日期：2016.7.27

  The first interrupted asymmetric hydroaminomethylation reaction was developed. The challenging trans-1,2-disubstituted olefins were employed as substrates, and a series of valuable chiral pyrrolidinones and pyrrolidines were obtained in high yields with high regioselectivities and excellent enantioselectivities. Several synthetic transformations were conducted, demonstrating the high synthetic utility

  开发了第一个间断的不对称氢氨甲基化反应。具有挑战性的反式-1,2-二取代烯烃被用作底物，并以高产率、高区域选择性和优异的对映选择性获得了一系列有价值的手性吡咯烷酮和吡咯烷。进行了几次合成转化，证明了我们方法的高合成效用。还开发了合成 vernakalant 和 Enablex 的创造性路线。
• Rh(III)-Catalyzed C–H Activation-Initiated Directed Cyclopropanation of Allylic Alcohols
  作者：Erik J. T. Phipps、Tomislav Rovis

  DOI：10.1021/jacs.9b02156

  日期：2019.5.1

  annulation onto allylic alcohols initiated by alkenyl C-H activation of N-enoxyphthalimides to furnish substituted cyclopropyl-ketones. Notably, the traceless oxyphthalimide handle serves three functions: directing C-H activation, oxidation of Rh(III), and, collectively with the allylic alcohol, in directing cyclopropanation to control diastereoselectivity. Allylic alcohols are shown to be highly reactive

  我们已经开发了一种 Rh(III) 催化的非对映选择性 [2+1] 环化到烯丙醇上，由 N-烯氧基邻苯二甲酰亚胺的烯基 CH 活化引发，以提供取代的环丙基酮。值得注意的是，无痕氧邻苯二甲酰亚胺手柄具有三个功能：引导 CH 活化、Rh(III) 的氧化，以及与烯丙醇共同引导环丙烷化以控制非对映选择性。烯丙醇被证明是高度反应性的烯烃偶联伙伴，导致定向的非对映选择性环丙烷化反应，提供其他途径无法获得的产物。
• Retro-Cope eliminations in the synthesis of 1,2,5-oxadiazinanes from allylamines and nitrones: a method for the amination of unactivated alkenes
  作者：Michael B. Gravestock、David W. Knight、Steven R. Thornton

  DOI：10.1039/c39930000169

  日期：——

  Heating an allylamine (e.g.9) and a nitrone (e.g.10) in an inert solvent produces often excellent yields of a 1,2,5-oxadiazinane (e.g.11) by a pathway which features a retro-Cope elimination and a Meisenheimer rearrangement; reduction of the oxadiazinanes leads to vicinal diamines and hence overall amination of the alkene function in the original allylamine.

  在惰性溶剂中加热烯丙胺（例如9）和硝酮（例如10）通常会通过具有逆向交配消除和迈森海默重排的途径产生极佳的1,2,5-恶二嗪烷（例如11）收率；恶二氮嗪酮的还原导致邻位二胺，因此使原始烯丙胺中的烯烃功能整体胺化。