N-benzylpent-4-enamide | 58170-50-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: N-benzylpent-4-enamide
• CAS: 58170-50-6
• 化学式: C₁₂H₁₅NO
• mdl: MFCD24392369
• 分子量: 189.257
• InChiKey: ALWCUSIXVLVYPM-UHFFFAOYSA-N

物化性质

• 沸点：
  365.5±31.0 °C(Predicted)
• 密度：
  0.999±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzylpent-4-enamide 在 三(三苯基膦)羰基氢化铑 lithium aluminium tetrahydride 、 氢气 、 三环己基膦 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 100.0 ℃ 、6.2 MPa 条件下， 反应 21.0h， 生成 1-benzylazepane
  参考文献：
  名称：

  Syntheses of nitrogen heterocycles by means of amine-directed carbonylation and hydrocarbonylation

  摘要：

  Amine-directed carbonylation of 2-allylpiperidine (5) gives 8-methyl-1-azabicyclo[4.3.0]nonan-9-one (7) with extremely high regio- and stereoselectivity, which is promoted by a stoichiometric amount of [RhCl(CO)2]2 in the presence of hydrogen chloride. A catalytic version of this process is developed, which converts 5-benzylamino-1-pentene (9) to 1-benzyl-3-methyl-2-piperidinone (10) selectively. Novel aminocarbocyclization of 9 gives 1-benzyl-3-methylpiperidine (12) or 1-benzylazepane (13) exclusively by employing appropriate hydrocarbonylation conditions. The scope and limitation of these new processes are discussed.

  DOI：

  10.1016/0022-328x(93)83252-q
• 作为产物：
  描述：

  [Benzyl(pent-4-enoyl)amino] methyl carbonate 在 copper(II) bis(trifluoromethanesulfonate) 敌草腈 作用下， 以 乙腈 为溶剂， 反应 48.0h， 以77%的产率得到N-benzylpent-4-enamide
  参考文献：
  名称：

  Tandem Cyclisations of Amidyl Radicals Derived from O-Acyl Hydroxamic Acid Derivatives

  摘要：

  由三丁基锡烷介导的 O-酰基异羟肟酸衍生物 5a-b 均裂产生的酰胺自由基经历串联环化，分别得到吡咯齐啶酮 6a-c 和吲哚齐啶酮 7a-b，而 5c-d 经历单环化，分别得到 β-内酰胺 10a 和 γ-内酰胺 11a 。另一方面，5d-f与Cu(OTf)2/DBN的反应提供还原10b、单环化10a和串联环化9产物的混合物，其比例取决于O-酰基的性质以及所用溶剂和浓度。

  DOI：

  10.1055/s-1999-2641

文献信息

• Diethylzinc-Mediated Radical 1,2-Addition of Alkenes and Alkynes
  作者：Xin Li、Songtao He、Qiuling Song

  DOI：10.1021/acs.orglett.1c00669

  日期：2021.4.16

  A novel diethylzinc-mediated radical 1,2-addition of perfluoroalkyl iodides to unactivated alkenes and alkynes is presented, which demonstrates a novel way to generate an ethyl difluoroacetate radical. This method is highly efficient and gives full conversions of the substrates, high yields of the products, and negligible byproducts and requires no column chromatography purifications. The mild conditions

  提出了一种新颖的由二乙基锌介导的全氟烷基碘与非活化烯烃和炔烃进行的1,2-基自由基加成反应，这表明了一种生成二氟乙酸乙酯基团的新方法。该方法非常高效，可实现底物的完全转化，产物的高收率和可忽略的副产物，并且不需要柱色谱法纯化。温和的条件使该协议能够表现出出色的官能团兼容性。
• Iridium-Catalyzed Aerobic α,β-Dehydrogenation of γ,δ-Unsaturated Amides and Acids: Activation of Both α- and β-C–H bonds through an Allyl–Iridium Intermediate
  作者：Zhen Wang、Zhiqi He、Linrui Zhang、Yong Huang

  DOI：10.1021/jacs.7b11351

  日期：2018.1.17

  Direct aerobic α,β-dehydrogenation of γ,δ-unsaturated amides and acids using a simple iridium/copper relay catalysis system is described. We developed a new strategy that overcomes the challenging issue associated with the low α-acidity of amides and acids. Instead of α-C-H metalation, this reaction proceeds by β-C-H activation, which results in enhanced α-acidity. Conjugated dienamides and dienoic acids

  描述了使用简单的铱/铜中继催化系统对 γ,δ-不饱和酰胺和酸进行直接有氧 α,β-脱氢。我们开发了一种新策略来克服与酰胺和酸的低 α 酸度相关的挑战性问题。该反应不是 α-CH 金属化，而是通过 β-CH 活化进行，从而导致 α-酸性增强。共轭二酰胺和二烯酸通过该反应以优异的产率合成，该反应使用简单的反应方案。机理实验表明催化剂静止状态机制，其中 α-CH 和 β-CH 裂解都被加速。
• The versatile conversion of acyclic amides to α-alkylated amines
  作者：Young-Ger Suh、Dong-Yun Shin、Jae-Kyung Jung、Seok-Ho Kim

  DOI：10.1039/b201719a

  日期：2002.5.9

  A general and efficient method for the versatile functionalization of acyclic amide via N,O-acetal TMS ether, an excellent precursor for the N-acyliminium ion, has been developed.

  已经开发了一种通用且有效的方法，用于通过N，O-缩醛TMS醚（一种出色的N-酰基酰亚胺离子的前体）对无环酰胺进行通用官能化。
• Triethylborane-Induced Radical Allylation Reaction with Zirconocene−Olefin Complex
  作者：Koji Hirano、Kazuya Fujita、Hiroshi Shinokubo、Koichiro Oshima

  DOI：10.1021/ol036431e

  日期：2004.2.1

  [reaction: see text] Allylzirconium reagents are effective for radical allylation of alpha-halo carbonyl compounds. The key steps would be homolytic cleavage of the zirconium-carbon bond and halogen abstraction by the resulting Cp(2)ZrCl(III). Zirconocene-olefin complex can be also utilized for the allylation of alpha-halo compounds.

  [反应：见正文]烯丙基锆试剂可有效地使α-卤代羰基化合物自由基烯丙基化。关键步骤将是锆-碳键的均质裂解和所得Cp（2）ZrCl（III）的卤素抽象。锆茂-烯烃配合物也可用于α-卤代化合物的烯丙基化。
• Enantioselective Synthesis of Cyclic Secondary Amines through Mo-Catalyzed Asymmetric Ring-Closing Metathesis (ARCM)
  作者：Sarah J. Dolman、Richard R. Schrock、Amir H. Hoveyda

  DOI：10.1021/ol036026n

  日期：2003.12.1

  Carbocyclic amines are synthesized efficiently in up to 93% ee by asymmetric ring-closing metathesis (ARCM) with 2-5 mol % chiral Mo complexes. An example is provided where the catalyst is prepared in situ (catalyst isolation not needed) to afford secondary amines that cannot be prepared by alternative methods. [reaction: see text]

  通过具有2-5 mol％手性Mo络合物的不对称闭环复分解（ARCM），可以最高达93％ee高效地合成碳环胺。提供了一个实例，其中就地制备催化剂（不需要分离催化剂）以提供不能通过替代方法制备的仲胺。[反应：看文字]