5-(2-甲苯基)戊-2-酮 | 103094-50-4

• 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: 5-(2-甲苯基)戊-2-酮
• 英文名称: 5-(2-tolyl)pentan-2-one
• 英文别名: 5-(o-tolyl)pentan-2-one；5-(2-methylphenyl)pentan-2-one
• CAS: 103094-50-4
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: ANPOAGZGOXZZQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-(2-甲苯基)戊-2-酮 以29%的产率得到
  参考文献：
  名称：

  SHONO TATSUYA; KISE NAOKI; SUZUMOTO TAKESHI; MORIMOTO TOSHIO, J. AMER. CHEM. SOC., 108,(1986) N 15, 4676-4677

  摘要：

  DOI：
• 作为产物：
  描述：

  邻甲基苯乙基溴 、 乙酰乙酸乙酯 生成 5-(2-甲苯基)戊-2-酮
  参考文献：
  名称：

  Electroreductive intramolecular coupling of nonconjugated aromatic ketones

  摘要：

  The electroreduction of nonconjugated aromatic ketones gave intramolecularly coupled products. The best result was obtained using an Sn cathode in i-PrOH containing tetraalkylammonium salt as a supporting electrolyte. This reductive cyclization proceeded with remarkable stereoselectivity, and the cis isomer was obtained exclusively. A variety of new bi- and polycyclic compounds were synthesized. The reaction mechanism was studied, and it was suggested that the anion radical generated by one-electron transfer to a carbonyl group attacks an aromatic ring intramolecularly. The choice of counter cation of the anion radical was critical for the reductive cyclization. Other reductive methods employing metal reducing agents were also studied. Reduction with Na in HMPA-THF gave the same cyclized product, though the yield was lower than that with the electroreduction.

  DOI：

  10.1021/jo00085a033

文献信息

• Aerobic Oxidative Dehydrogenation of Ketones to 1,4-Enediones
  作者：Bao-Yin Zhao、Xing-Long Zhang、Rui-Li Guo、Meng-Yue Wang、Ya-Ru Gao、Yong-Qiang Wang

  DOI：10.1021/acs.orglett.0c04174

  日期：2021.2.19

  An efficient and unprecedented strategy for the synthesis of 1,4-enediones from saturated ketones has been developed via palladium-catalyzed oxidative dehydrogenation. The protocol employs molecular oxygen as the sole oxidant and represents an atom- and step-economic process. The approach showed broad substrate scope, good functional group tolerance, and complete E-stereoselectivity. The reaction mechanism

  通过钯催化的氧化脱氢，已经开发出一种有效且空前的从饱和酮合成1,4-二烯酮的策略。该协议采用分子氧作为唯一的氧化剂，代表了原子经济和逐步经济的过程。该方法显示出广泛的底物范围，良好的官能团耐受性和完全的E-立体选择性。通过氘标记实验和中间实验研究了反应机理。
• Methylene C(sp³)–H Arylation of Aliphatic Ketones Using a Transient Directing Group
  作者：Kai Hong、Hojoon Park、Jin-Quan Yu

  DOI：10.1021/acscatal.7b02905

  日期：2017.10.6

  Palladium-catalyzed methylene β-C(sp3)–H arylation of aliphatic ketones using a transient directing group is developed. The use of α-benzyl β-alanine directing group that forms a six-membered chelation with palladium is crucial for promoting the methylene C(sp3)–H bond activation.

  开发了使用瞬态导向基团的钯催化脂族酮的亚甲基β-C（sp 3）–H芳基化反应。与钯形成六元螯合的α-苄基β-丙氨酸引导基团的使用对于促进亚甲基C（sp 3）–H键的活化至关重要。
• 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。
• Samarium Diiodide Mediated Ketyl-Aryl Coupling Reactions - Influence of Substituents and Trapping Experiments
  作者：Ulrike K. Wefelscheid、Mathias Berndt、Hans-Ulrich Reißig

  DOI：10.1002/ejoc.200800293

  日期：2008.7

  derivatives as single diastereoisomers in most cases. The position of the substituents was also of crucial influence on the outcome; in several cases ipso-substitution leading to the formation of spiro compounds was observed. Electron-donating substituents at the aromatic moiety are less favourable for the ketyl–aryl couplings. They apparently impede the second electron transfer that is involved in this multi-step

  这项综合研究描述了芳基部分的取代基对 SmI2 介导的分子内酮基-芳基偶联反应的影响。不同取代的γ-芳基酮被用作前体，其通过4-戊烯-2-醇与相应的溴苯或碘苯的Heck反应直接制备。在用两当量的二碘化钐γ-芳基酮处理后，带有吸电子取代基，如氰基、三氟甲基或羰基，在大多数情况下，得到预期的六氢化萘衍生物，为单一的非对映异构体。取代基的位置对结果也有至关重要的影响。在一些情况下，观察到导致形成螺环化合物的 ipso 取代。芳族部分的给电子取代基对酮基-芳基偶联不太有利。它们显然阻碍了这个多步骤过程中涉及的第二次电子转移。在这些观察的基础上，详细讨论了 促进的酮基-芳基偶联的机制。对于在间位具有吸电子取代基的前体， 促进的环化的相当稳定的碳负离子中间体可以用丙酮或烯丙基溴作为亲电试剂捕获，以区域选择性地提供相应的加成产物。我们的结果对于立体选择性生成的六氢化萘衍生物的合成应用应该是有价值的。（©
• Heck Reaction of Aryl Bromides with Pent-4-en-2-ol, 2-Phenylpent-4-en-2-ol, or Hept-6-en-3-ol Catalysed by a Palladium-Tetraphosphine Complex
  作者：Henri Doucet、Maurice Santelli、Florian Berthiol

  DOI：10.1055/s-2005-918427

  日期：——

  depends on the substituents on the aryl bromide and on the base. Sterically congested and electron-rich aryl bromides gave selectively the linear ketones by migration of the double bond. With electron-poor aryl bromides, the formation of large amounts of (E)-arylalk-1-enol derivatives or side products was observed in some cases. Similar reactions rates were observed with electron-poor and electron-rich

  四膦cis,cis,cis-1,2,3,4-四(二苯基膦甲基)环戊烷与[Pd(η 3 -C 3 H 5 )Cl] 2 组合为芳基溴化物的Heck反应提供了非常有效的催化剂与 pent-4-en-2-ol、2-phenylpent-4-en-2-ol 或 hept-6-en-3-ol。对于 pent-4-en-2-ol 或 hept-6-en-3-ol，有利于形成 5-arylpentan-2-one 或 7-arylheptan-3-one 衍生物的选择性分别取决于在芳基溴和碱基上的取代基上。空间拥挤和富电子的芳基溴化物通过双键的迁移选择性地产生线性酮。对于缺电子芳基溴化物，在某些情况下观察到大量 (E)-arylalk-1-enol 衍生物或副产物的形成。用贫电子和富电子芳基溴观察到类似的反应速率。几个反应可以用低至 0.01% 的催化剂进行。芳基溴化物上可以有多种取代基，例如甲氧基、二