5-己炔酰胺,N-(苯基甲基)- | 155193-71-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 5-己炔酰胺,N-(苯基甲基)-
• 英文名称: N-benzylhex-5-ynamide
• CAS: 155193-71-8
• 化学式: C₁₃H₁₅NO
• 分子量: 201.268
• InChiKey: GLNUPYVOYQDLLD-UHFFFAOYSA-N

物化性质

• 沸点：
  393.5±35.0 °C(Predicted)
• 密度：
  1.034±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  5-己炔酰胺,N-(苯基甲基)- 在 [N-isopropyl-2-(isopropylamino)troponiminato]methylzinc 作用下， 以 氘代苯 为溶剂， 反应 60.0h， 生成 1-benzyl-6-methylenepiperidin-2-one
  参考文献：
  名称：

  用均相锌催化剂进行官能化烯烃和炔烃的分子内加氢胺化。

  摘要：

  DOI：

  10.1002/anie.200502006
• 作为产物：
  描述：

  5-己炔酸 以 乙醚 为溶剂， 反应 6.0h， 生成 5-己炔酰胺,N-(苯基甲基)-
  参考文献：
  名称：

  Studies on the Intramolecular Cycloaddition Reaction of Mesoionics Derived from the Rhodium(II)-Catalyzed Cyclization of Diazoimides

  摘要：

  A series of alkenyl-substituted imides were prepared by treating the appropriate amide with 2,2,6-trimethyl-4H-1,3-dioxen-4-one in xylene at 140-degrees-C to give the N-acetoacylated imides. Exposure of these imides to standard diazo transfer conditions gave the desired diazoimides. The carbenoid intermediate derived by treatment of the diazoimide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen atom to generate an isomunchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography. The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring pi-bond across the transient isomunchnone dipole. Molecular mechanics calculations were used to model energy differences between the endo and exo diastereomers. The calculations reveal that the endo diastereomers are significantly (8-12 kcal/mol) lower in energy than the corresponding exo isomers thereby providing a rationale for the preferred endo cycloaddition. Ring opening of the cycloadducts occurred readily producing a transient N-acyliminium ion which either lost a proton to give an enamide or was reduced by Et3SiH to afford a bicyclic piperidine ring.

  DOI：

  10.1021/jo00085a035

文献信息

• Highly Efficient and Regioselective Platinum(II)-Catalyzed Tandem Synthesis of Multiply Substituted Indolines and Tetrahydroquinolines
  作者：Xin-Yuan Liu、Chi-Ming Che

  DOI：10.1002/anie.200805383

  日期：2009.3.16

  special advantage: The platinum(II)‐catalyzed tandem cyclization of aminoalkynes with 1,3‐diketones offers a new and highly efficient method for the synthesis of indolines and tetrahydroquinolines (see scheme; M.S.=molecular sieves). This transformation affords good to excellent product yields with high regio‐ and chemoselectivity under mild reaction conditions.

  一个特殊的优势：带有1,3-二酮的铂（Ⅱ）催化的氨基炔的串联环化为合成二氢吲哚和四氢喹啉提供了一种高效的新方法（见方案； MS =分子筛）。在温和的反应条件下，这种转化可提供良好的产品收率，具有很高的区域选择性和化学选择性。
• Broad-Spectrum Catalysts for the Ambient Temperature Anti-Markovnikov Hydration of Alkynes
  作者：Le Li、Mingshuo Zeng、Seth B. Herzon

  DOI：10.1002/anie.201404320

  日期：2014.7.21

  Anti‐Markovnikov alkyne hydration provides a valuable route to aldehydes. Half‐sandwich ruthenium complexes ligated by 5,5′‐bis(trifluoromethyl)‐2,2′‐bipyridine are remarkably active for this transformation. In the presence of 2 mol % metal, a wide range of functionalized aliphatic and aromatic alkynes are hydrated in high yield at ambient temperature.

  抗马尔科夫尼科夫炔烃水合为醛的合成提供了有价值的途径。由5,5'-双（三氟甲基）-2,2'-联吡啶连接的半三明治钌络合物对于该转化非常有效。在2mol％金属的存在下，在环境温度下高产率地将多种官能化的脂族和芳族炔烃水合。
• Temporal separation of catalytic activities allows anti-Markovnikov reductive functionalization of terminal alkynes
  作者：Le Li、Seth B. Herzon

  DOI：10.1038/nchem.1799

  日期：2014.1

  There is currently great interest in the development of multistep catalytic processes in which one or several catalysts act sequentially to rapidly build complex molecular structures. Many enzymes—often the inspiration for new synthetic transformations—are capable of processing a single substrate through a chain of discrete, mechanistically distinct catalytic steps. Here, we describe an approach to emulate the efficiency of these natural reaction cascades within a synthetic catalyst by the temporal separation of catalytic activities. In this approach, a single catalyst exhibits multiple catalytic activities sequentially, allowing for the efficient processing of a substrate through a cascade pathway. Application of this design strategy has led to the development of a method to effect the anti-Markovnikov (linear-selective) reductive functionalization of terminal alkynes. The strategy of temporal separation may facilitate the development of other efficient synthetic reaction cascades. Multifunctional catalysts typically process substrates and intermediates concurrently. Here, a strategy is described to separate catalytic activities in the time domain (temporal separation). Application of this strategy has led to the development of a method to effect the anti-Markovnikov reductive functionalization of terminal alkynes; such an approach may facilitate the development of other synthetic reaction cascades.

  目前，发展多步催化过程备受关注，其中一个或多个催化剂按顺序作用，以快速构建复杂分子结构。许多酶——通常是新合成转化的灵感来源——能够通过一系列离散的、机制上不同的催化步骤处理单一底物。在这里，我们描述了一种通过催化活性的时间分离来模拟这些自然反应级联的效率的方法。在这种方法中，单一催化剂按顺序展现多种催化活性，从而允许有效地通过级联路径处理底物。该设计策略的应用促成了一种方法，以实现末端炔烃的反马尔科夫尼科夫（线性选择性）还原官能化。时间分离的策略可能会促进其他高效合成反应级联的发展。多功能催化剂通常同时处理底物和中间体。在这里，描述了一种在时间领域分离催化活性的策略（时间分离）。该策略的应用促成了一种方法，以实现末端炔烃的反马尔科夫尼科夫还原官能化；如此方法可能会促进其他合成反应级联的发展。
• A Highly Active and Air-Stable Ruthenium Complex for the Ambient Temperature Anti-Markovnikov Reductive Hydration of Terminal Alkynes
  作者：Mingshuo Zeng、Le Li、Seth B. Herzon

  DOI：10.1021/ja501738a

  日期：2014.5.14

  partially dissociated from the ruthenium center (by protonation) in the reaction media, thereby generating a vacant coordination site for catalysis. These studies also show that this substituent increases hydrogenation activity by promoting activation of the reductant. At least three catalytic cycles, involving the decarboxylation of formic acid, hydration of the alkyne, and hydrogenation of the intermediate

  通过直接添加基于杂原子的亲核试剂将末端炔烃转化为功能化产物是催化的一个重要目标。我们报告了半夹心钌配合物 12 的设计、合成和机理研究，它是炔烃的反马尔科夫尼科夫还原水合的高活性催化剂。12 的关键设计元素涉及一个三齿氮基配体，其中包含一个半稳定的 3-（二甲氨基）丙基取代基。在中性条件下，二甲氨基取代基与钌中心协调，生成空气稳定的 18 电子 κ(3) 复合物。机理研究表明，二甲氨基取代基在反应介质中从钌中心部分解离（通过质子化），从而产生用于催化的空配位点。这些研究还表明，该取代基通过促进还原剂的活化来提高氢化活性。至少三个催化循环，包括甲酸的脱羧、炔烃的水合和中间体醛的氢化，在由 12 介导的反应中同时运行。 使用少至 2在环境温度下 mol % 为 12，并且配合物 12 在空气中稳定至少两周。本文概述的研究将 12 确立为迄今为止发现的用于反马尔科夫尼科夫还原水合的最活跃和最实用的催化剂，定义了
• Selective modification of alkyne-linked peptides and proteins by cyclometalated gold(III) (C^N) complex-mediated alkynylation
  作者：Hok-Ming Ko、Jie-Ren Deng、Jian-Fang Cui、Karen Ka-Yan Kung、Yun-Chung Leung、Man-Kin Wong

  DOI：10.1016/j.bmc.2020.115375

  日期：2020.4

  reaction of 6-membered ring cyclometalated gold(III) (C^N) complexes (HC^N = 2-arylpyridines) with terminal alkynes. Screening of the reaction conditions with a series of cyclometalated gold(III) complexes with phenylacetylene gave an excellent yield (up to 82%) by conducting the reaction in slightly alkaline aqueous conditions. The reaction scope was expanded to various alkynes, including alkyne-linked

  炔烃是掺入蛋白质中的有用功能，用于位点选择性生物缀合反应。尽管有效的生物共轭反应是最常见的方法，例如炔烃和叠氮化物的铜（I）催化和/或无铜的1,3-偶极环加成反应，但新的基于炔烃的生物共轭反应的开发仍是化学领域的一个持续兴趣。生物学。在这项工作中，已开发出一种新方法，用于通过六元环环金属化金（III）（C ^ N）络合物（HC ^）的交叉偶联反应形成芳基乙炔，选择性修饰炔烃连接的肽和蛋白质。 N ＝ 2-芳基吡啶）与末端炔烃。通过在弱碱性水溶液条件下进行反应，用一系列带有苯乙炔的环金属化金（III）配合物筛选反应条件，可得到优异的收率（最高82％）。反应范围扩大到各种炔烃，包括炔烃连接的肽，可实现高达> 99％的转化率。使用荧光丹磺酰基（1l）和BODIPY（1m）连接的金（III）配合物，已对炔烃连接的溶菌酶进行了选择性修饰。