苯乙酰胺,N-2-炔丙基- | 174271-37-5

• 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: 苯乙酰胺,N-2-炔丙基-
• 英文名称: 2-phenyl-N-(prop-2-yn-1-yl)acetamide
• 英文别名: 2-phenyl-N-(prop-2-ynyl)acetamide；2-Phenyl-N-(2-propyn-1-YL)acetamide；2-phenyl-N-prop-2-ynylacetamide
• CAS: 174271-37-5
• 化学式: C₁₁H₁₁NO
• mdl: MFCD14631315
• 分子量: 173.214
• InChiKey: HSPQVQUHIDEEQI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.181
• 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：

  苯乙酰胺,N-2-炔丙基- 在 四氯化碳 、 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 以56%的产率得到苯乙酰腈,a-2-亚丙烯基-
  参考文献：
  名称：

  Rearrangements of Substituted 3-Aza-1,2,5-hexatrienes. 3. The Scope and Versatility of an Extremely Mild 3-Aza-Cope Reaction

  摘要：

  An investigation of the [3,3]-sigmatropic reaction of substituted 3-aza-1,2,5-hexatrienes to give 4-pentenenitriles is presented. This reaction has been found to occur under a wide variety of reactions conditions (10 are reported) starting from readily available N-allylamides. In contrast to other 3-aza-Cope reactions, this process occurs at room temperature, under essentially neutral conditions, allowing for the facile preparation of substituted nitrile products in moderate to excellent yields. The scope and versatility of this reaction are demonstrated by its use on a wide variety of substrates, including nitrogen- and oxygen-substituted amides. The rearrangements of cis- and trans-4-tert-butyl-N-allylcyclohexanecarboxamides 16a and 16b are reported and were found to give a ratio of axial to equatorial (A:E) products consistent with A:E ratios found for other related sigmatropic reactions. The stereochemical requirements for this reaction appear to be similar to other [3,3]-rearrangements even though the transition state for this rearrangement is most likely neither boat nor chairlike.

  DOI：

  10.1021/jo951587g
• 作为产物：
  描述：

  2-phenyl-N-[3-(tert-butyl(diphenyl)silyl)prop-2-ynyl]acetamide 在 四丁基氟化铵 、 盐酸 、 水 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 0.25h， 生成 苯乙酰胺,N-2-炔丙基-
  参考文献：
  名称：

  Click à la carte: robust semi-orthogonal alkyne protecting groups for multiple successive azide/alkyne cycloadditions

  摘要：

  We herein describe an in-depth screening and systematic comparison of five classical silyl alkyne protective groups, to evaluate their potential in the context of multiple successive copper (I)-catalyzed alkyne-azide cycloadditions (CuAAC). We confirm the relative sensitivity of TMS, especially under CuAAC conditions. The relative robustness of its higher analogues, and the discovery of mild silver-catalyzed deprotection conditions selective for TES compared to DPS or TIPS allowed us to design a strategy allowing three successive CuAAC on a single scaffold, as we have illustrated by the synthesis of a tris-triazolo model compound. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.06.093

文献信息

• Sterically Demanding Oxidative Amidation of α-Substituted Malononitriles with Amines Using O₂
  作者：Jing Li、Martin J. Lear、Yujiro Hayashi

  DOI：10.1002/anie.201603399

  日期：2016.7.25

  An efficient amidation method between readily available 1,1-dicyanoalkanes and either chiral or nonchiral amines was realized simply with molecular oxygen and a carbonate base. This oxidative protocol can be applied to both sterically and electronically challenging substrates in a highly chemoselective, practical, and rapid manner. The use of cyclopropyl and thioether substrates support the radical

  简单地使用分子氧和碳酸盐碱即可实现易于获得的1,1-二氰基烷烃与手性或非手性胺之间的高效酰胺化方法。该氧化方案可以高度化学选择性，实用和快速的方式应用于空间和电子挑战性底物。环丙基和硫醚底物的使用可支持α-过氧丙二腈物种的自由基形成，后者可以环化成二恶英，后者可以单价氧化丙二腈α-碳二酮以提供能够与胺亲核试剂反应的活化的酰基氰化物。
• Umpolung reactivity in amide and peptide synthesis
  作者：Bo Shen、Dawn M. Makley、Jeffrey N. Johnston

  DOI：10.1038/nature09125

  日期：2010.6

  which the polarities of the two reactants are reversed (German, umpolung) during carbon–nitrogen bond formation relative to traditional approaches. The use of nitroalkanes as acyl anion equivalents provides a conceptually innovative approach to amide and peptide synthesis, and one that might ultimately provide for efficient peptide synthesis that is fully reliant on enantioselective methods.

  酰胺键是自然界最常见的功能和结构元素之一，因为所有天然肽和蛋白质的骨架都由酰胺键组成。酰胺也存在于许多治疗性小分子中。使用现有方法构建酰胺键主要依赖于脱水方法，尽管氧化和基于自由基的方法是代表性的替代方法。在几乎每个例子中，在碳-氮键形成步骤中，碳和氮分别具有亲电和亲核特性。在这里，我们表明用亲电碘源活化胺和硝基烷烃可以直接产生酰胺产物。初步观察支持两种反应物极性反转的机制（德国，umpolung) 在碳氮键形成过程中相对于传统方法。使用硝基烷烃作为酰基阴离子等价物为酰胺和肽合成提供了一种概念上的创新方法，并且可能最终提供完全依赖对映选择性方法的有效肽合成。
• Cu(I)-Catalyzed Synthesis of Dihydropyrimidin-4-ones toward the Preparation of β- and β³-Amino Acid Analogues
  作者：Basker Rajagopal、Ying-Yu Chen、Chun-Chi Chen、Xuan-Yu Liu、Huei-Ren Wang、Po-Chiao Lin

  DOI：10.1021/jo402670d

  日期：2014.2.7

  A copper(I)-catalyzed synthesis of substituted dihydropyrimidin-4-ones from propargyl amides via the formation of ketenimine intermediate has been successfully developed; the synthesis afforded good isolated yields (80–95%). The mild reaction conditions at room temperature allow the reaction to proceed to completion in a few hours without altering the stereochemistry. Further, by involving a variety

  已经成功地开发了铜（I）催化炔酮胺中间体从炔丙基酰胺合成取代的二氢嘧啶-4-酮。合成得到良好的分离产率（80-95％）。室温下温和的反应条件可使反应在数小时内完成，而无需改变立体化学。另外，通过涉及多种反应性亲核试剂，将得到的被取代的二氢嘧啶-4-酮被优雅转化成相应的β-和β 3 -氨基酸的类似物。
• Cyclization of Propargylic Amides: Mild Access to Oxazole Derivatives
  作者：Jan P. Weyrauch、A. Stephen K. Hashmi、Andreas Schuster、Tobias Hengst、Stefanie Schetter、Anna Littmann、Matthias Rudolph、Melissa Hamzic、Jorge Visus、Frank Rominger、Wolfgang Frey、Jan W. Bats

  DOI：10.1002/chem.200902472

  日期：2010.1.18

  the oxazole synthesis were developed and chelate ligands can be obtained. The use of Barluenga’s reagent offers a new and mild access to the synthetically valuable iodoalkylideneoxazoles from propargylic amides, this reagent being superior to other sources of halogens.

  研究了底物范围，金催化的恶唑合成的机理以及在侧链上具有不同脂族，芳族和官能团的底物。甚至具有多个炔丙基酰胺基团的分子也可以轻松转化，从而提供具有令人感兴趣的光学特性的二恶唑和三恶唑。此外，还研究了金（I）催化亚烷基的合成范围。这些恶唑合成的可分离中间体的进一步官能化得到了发展，并可以获得螯合配体。Barluenga试剂的使用为从炔丙基酰胺获得具有合成价值的碘代亚烷基新恶唑提供了一种新的，温和的途径，该试剂优于其他卤素来源。
• Ruthenium-Catalyzed Oxidative Amidation of Alkynes to Amides
  作者：Andrea Álvarez-Pérez、Miguel A. Esteruelas、Susana Izquierdo、Jesús A. Varela、Carlos Saá

  DOI：10.1021/acs.orglett.9b01993

  日期：2019.7.5

  Complex CpRuCl(PPh3)2 catalyzes reactions of terminal alkynes with 4-picoline N-oxide and primary and secondary amines to afford the corresponding amides. The reactions occur in chlorinated solvent and aqueous medium, showing applications in peptide chemistry. Stoichiometric studies reveal that the true catalysts of the processes are the vinylidene cations [CpRu(═C═CHR)(PPh3)2]+ which are oxidized

  络合物CpRuCl（PPh 3）2催化末端炔烃与4-甲基吡啶N-氧化物以及伯胺和仲胺的反应，得到相应的酰胺。反应发生在氯化溶剂和水性介质中，显示出在肽化学中的应用。化学计量的研究表明，该工艺的真正的催化剂是亚乙烯基的阳离子[CPRU（═C═CHR）（PPH 3）2 ] +，其被氧化成的Ru（η 2由-CO）-ketenes Ñ氧化物。最后，伯胺和仲胺向游离酮的亲核加成产生相应的酰胺。