N-benzyl-N-(propa-1,2-dien-1-yl)acetamide | 137518-30-0

• 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: N-benzyl-N-(propa-1,2-dien-1-yl)acetamide
• CAS: 137518-30-0
• 化学式: C₁₂H₁₃NO
• 分子量: 187.241
• InChiKey: PAQPSUBVBUQHSV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzyl-N-(propa-1,2-dien-1-yl)acetamide 在 fac-tris(2-phenylpyridinato-N,C2')iridium(III) 、 萘 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以56 %的产率得到1-((3as,6s)-6,7-dihydro-3a,6-ethenoisoindol-2(3H)-yl)ethan-1-one
  参考文献：
  名称：

  可见光促进简单芳烃的分子内对环加成

  摘要：

  我们通过空间和电子无偏芳基片段的脱芳构化展示了桥接自行车的首次合成。可见光促进方法发生在室温下，具有足够的官能团耐受性。芳基伴侣双官能化的关键是使用萘作为添加剂，通过其扩展的 π 云稳定瞬态（双）自由基。这种效应可能导致它在激进序列中的广泛使用。

  DOI：

  10.1002/anie.202216817
• 作为产物：
  描述：

  苄胺 在 sodium hydride 、 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.5h， 生成 N-benzyl-N-(propa-1,2-dien-1-yl)acetamide
  参考文献：
  名称：

  Nickel-Catalyzed Synthesis of Stereochemically Defined Enamides via Bi- and Tricomponent Coupling Reaction

  摘要：

  The stereoseleetive synthesis of (E)-trisubstituted tertiary enamides is documented via site-selective Ni-catalyzed beta-arylation of allenamides with boronic acids in high yields (up to 89%). The nucleophilic character of the "organo-Ni" intermediates is further exploited to implement a one-pot tricomponent procedure involving the final allylation of aldehydes (yields up to 93%). Mechanistic insights and efficiency on a gram scale process were also documented.

  DOI：

  10.1021/acs.orglett.7b02166

文献信息

• Copper-Catalyzed Hydroamination of Allenes: from Mechanistic Understanding to Methodology Development
  作者：Luca Alessandro Perego、Rémi Blieck、Antoine Groué、Florian Monnier、Marc Taillefer、Ilaria Ciofini、Laurence Grimaud

  DOI：10.1021/acscatal.7b00911

  日期：2017.7.7

  Experimental and theoretical mechanistic studies on the Cu(OTf)2-catalyzed hydroamination reaction of terminal allenes with secondary amines reveal that in situ generated cationic Cu(I) is the catalytically active species and explain the observed regio- and stereoselectivity for the unbranched E product. Insight into the structure of the relevant transition states allowed the generalization of this

  对末端异位烯与仲胺的Cu（OTf）2催化加氢胺化反应的实验和理论机理研究表明，原位生成的阳离子Cu（I）是催化活性物质，并解释了所观察到的对直链E产物的区域和立体选择性。对相关过渡态结构的洞察力使这种方法可以推广到前所未有的温和和耐官能团条件下的烯丙酰胺和N-烯丙基氨基甲酸酯。除电子作用外，酰胺氧的螯合作用也解释了这类底物的高固有反应性。
• PhI(OAc)2-mediated synthesis of propargylic N, O-acetals by 1, 2-addition of alcohols to allenamides
  作者：Ruohe Huang、Pengyu Xu、Weixiang Wang、Guo Peng、Hui Yu

  DOI：10.1016/j.tetlet.2020.151753

  日期：2020.4

  electrophilic activation of allenamides was investigated and propargylic N, O-acetals were prepared in moderate to good yields. By the use of PhI(OAc)2 as oxidant and alcohol as both nucleophile and solvent, allenamides were converted into propargylic N, O-acetals via 1, 2-addition of alcohol to the sulfimide ion intermediate, and no 1, 4-adducts were found.

  研究了高价碘介导的烯丙酰胺的亲电活化，并以中等至良好的产率制备炔丙基N，O-乙缩醛。通过使用PhI（OAc）2作为氧化剂，使用醇作为亲核试剂和溶剂，将烯丙基酰胺通过将1、2-醇加到亚磺酰亚胺离子中间体上而没有1，-4加合物转化为炔丙基N，O-缩醛。被发现。
• Studies Toward Improved Enantiocontrol in the Asymmetric Cu-Catalyzed Reductive Coupling of Ketones and Allenamides: 1,2-Aminoalcohol Synthesis
  作者：Stephen Collins、Joshua D. Sieber

  DOI：10.1021/acs.orglett.3c00157

  日期：2023.3.10

  Herein, we report the development of an improved system for the Cu-catalyzed enantioselective reductive coupling of ketones and allenamides through the optimization of the allenamide to avoid an on-cycle rearrangement. High enantioselectivities could be obtained for a variety of ketones. Use of the acyclic allenamides described herein selectively generated anti-diastereomers in contrast to cyclic allenamides

  在此，我们报告了一种改进的系统的开发，用于铜催化的酮类和丙二烯酰胺的对映选择性还原偶联，通过优化丙二烯酰胺以避免循环重排。对多种酮可以获得高对映选择性。使用本文所述的无环丙二烯酰胺选择性地产生反-非对映异构体，这与之前显示有利于顺式形式的环丙二烯酰胺形成对比。还介绍了这种非对映选择性变化的基本原理。
• Selective Hydrofunctionalization of <i>N</i>-Allenyl Derivatives with Heteronucleophiles Catalyzed by Brønsted Acids
  作者：Arianna Quintavalla、Davide Carboni、Alessandro Brusa、Marco Lombardo

  DOI：10.1021/acs.joc.3c02322

  日期：2024.2.16

  environmentally sustainable protocol for the γ-hydrofunctionalization of N-allenyl compounds using various heteronucleophiles catalyzed solely by simple Brønsted acids. The method displays remarkable attributes, highlighting its sustainability, efficiency, regio- and stereoselectivity, as well as its versatile applicability to diverse heteroatom-containing enamides. Notably, our approach eliminates the need

  在这项研究中，我们提出了一种新颖且环境可持续的方案，用于使用仅由简单的布朗斯台德酸催化的各种异核试剂对N -丙二烯基化合物进行 γ-氢官能化。该方法显示出显着的属性，突出了其可持续性、效率、区域选择性和立体选择性，以及对各种含杂原子烯酰胺的多功能适用性。值得注意的是，我们的方法消除了对金属催化剂和有毒溶剂的需求，代表了绿色化学实践的重大进步。我们通过成功地将反应扩大到克级合成来展示我们协议的广泛范围，强调其潜在工业实施的稳健性。由此产生的γ-杂取代烯酰胺为进一步合成转化提供了新的可能性，产生具有多种应用的高度功能化的化合物。机理研究揭示了 CSA 作为催化剂的关键作用，可以通过共价活化模式实现醇加成。
• Phenyl-substituted analogs of oxotremorine as muscarinic antagonists
  作者：Bjoern M. Nilsson、Hugo M. Vargas、Bjoern Ringdahl、Uli Hacksell

  DOI：10.1021/jm00080a013

  日期：1992.1

  A series of phenyl-substituted analogues of the muscarinic agent oxotremorine (1) have been prepared. The new compounds (3b-11b and 9c) were assayed for antimuscarinic activity on the isolated guinea pig ileum and in intact mice. They were also evaluated for ability to inhibit the binding of the muscarinic antagonist (-)-[H-3]-N-methylscopolamine to homogenates of the rat cerebral cortex. The phenyl-substituted derivatives were devoid of intrinsic muscarinic activity. Instead, they behaved as competitive muscarinic antagonists in these assays with similar or lower affinity for muscarinic receptors than the corresponding methyl-substituted analogues. The succinimide (8b) and the pyrrolidone (3b) derivatives of 1 substituted with a phenyl group at position 1 of the butynyl chain showed the highest antimuscarinic potency with dissociation constants (K(D)) of 0.10 and 0.20-mu-M, respectively, in the ileum assay. The phenyl-substituted analogues showed an approximately 10-fold lower in vivo antimuscarinic potency than their corresponding methyl-substituted positional isomers. A correlation was observed between in vitro and in vivo potency within subsets consisting of methyl- and phenyl-substituted derivatives.