3-(2,4,6-trimethylphenyl)-2-cyclohexen-1-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(2,4,6-trimethylphenyl)-2-cyclohexen-1-one
• 英文别名: 3-(2,4,6-Trimethylphenyl)cyclohex-2-en-1-one；3-(2,4,6-trimethylphenyl)cyclohex-2-en-1-one
• 化学式: C₁₅H₁₈O
• 分子量: 214.307
• InChiKey: URGYWETVGIABOG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-环己烯氧基三甲基硅烷 在 2,2'-联吡啶 、 氧气 、 palladium diacetate 作用下， 以 二甲基亚砜 为溶剂， 反应 13.0h， 生成 3-(2,4,6-trimethylphenyl)-2-cyclohexen-1-one
  参考文献：
  名称：

  检查通过 Pd (II) 介导的顺序脱氢硅烷化和芳基化从烯醇硅烷衍生 β-芳基烯酮作为酮当量的范围

  摘要：

  将甲硅烷基烯醇醚作为饱和酮的掩蔽源进行检测，通过脱氢硅烷化原位生成烯酮，然后使用中继 Pd(II) 催化在一锅中进行原位氧化芳基化和芳基硼酸作为金属转移偶联伙伴，从而衍生出 β-芳基烯酮及其衍生物。无碱基条件。氧气被发现是一种有效的绿色氧化剂，可以实现烯醇硅烷的脱氢硅烷化和芳基化。此外，芳基化条件可以定制设计，以利用芳基卤化物作为芳基化剂的替代来源。通过 35 个实例（收率高达 95%）研究了制备范围，并且机理研究暗示了基于阳离子 Pd(II) 的催化体系。

  DOI：

  10.1021/acs.joc.3c00502

文献信息

• Palladium-Catalyzed Oxidative Heck Coupling of Cyclic Enones with Simple Arenes by CH Activation
  作者：Leung Gulice Yiu Chung、Nur Asyikin Binte Juwaini、Jayasree Seayad

  DOI：10.1002/cctc.201500079

  日期：2015.4.20

  A simple catalyst system consisting of Pd(OAc)2 and 3‐nitropyridine for the aerobic oxidative Heck coupling of cyclic enones, in particular challenging unsubstituted cyclic enones, with simple arenes by CH activation was investigated. This novel method was applied to various functionalized arenes and cyclic enones and allowed the synthesis of β‐aryl cyclic enones in modest to high yields.

  研究了由Pd（OAc）2和3-硝基吡啶组成的简单催化剂体系，用于通过CH活化将简单的芳烃与环状烯酮，特别是具有挑战性的未取代环状烯酮进行好氧氧化Heck偶联。这种新方法被应用于各种功能化的芳烃和环状烯酮，并允许以中等至高收率合成β-芳基环状烯酮。
• Soluble Lanthanides as Mediators of the Stork–Danheiser Transposition Reaction
  作者：Samuel T. Hugie、Andrea Ambrosi

  DOI：10.1021/acs.organomet.3c00371

  日期：2023.11.13

  The reaction of organometallic reagents with vinylogous esters (Stork–Danheiser transposition) provides direct access to 3-substituted cyclic enones. However, the reaction typically fails with sterically hindered aryl or alkyl nucleophiles due to competing enolization. Cerium(III) chloride and other lanthanide salts have traditionally been used to mitigate the basicity and enhance the nucleophilic

  有机金属试剂与插烯酯的反应（Stork-Danheiser 转位）提供了直接获得 3-取代环烯酮的途径。然而，由于竞争性烯醇化，空间位阻芳基或烷基亲核试剂的反应通常会失败。氯化铈(III)和其他镧系元素盐传统上用于降低碱性并增强具有挑战性的亲核试剂的亲核行为。然而，根据我们的经验，使用 CeCl 3作为 Stork-Danheiser 转座的介体会导致重现性问题。我们在此描述了有机可溶性镧系元素（LnCl 3 /R 4 NX 和 LnCl 3 ·2LiCl）在促进几类有机镁试剂的 Stork-Danheiser 转座中的应用。
• Heck-Type Arylation of 2-Cycloalken-1-ones with Arylpalladium Intermediates Formed by Decarboxylative Palladation and by Aryl Iodide Insertion
  作者：Daisuke Tanaka、Andrew G. Myers

  DOI：10.1021/ol0363467

  日期：2004.2.1

  A palladium-catalyzed decarboxylative arylation reaction was shown to produce Heck-type coupling products using a number of different arene carboxylic acid and 2-cycloalken-1-one substrates. The more conventional Heck coupling of an aryl iodide and a 2-cycloalken-1-one reactant was also briefly explored for comparison, where it was found that phosphine-free (Jeffery) conditions afforded the highest yield of product.
• Development of a Decarboxylative Palladation Reaction and Its Use in a Heck-type Olefination of Arene Carboxylates
  作者：Andrew G. Myers、Daisuke Tanaka、Michael R. Mannion

  DOI：10.1021/ja027523m

  日期：2002.9.1

  The development of a palladium-catalyzed decarboxylative coupling reaction of arene carboxylates with olefinic substrates is described. The optimized procedure for decarboxylative palladation employs Pd(O2CCF3)2 as catalyst (0.2 equiv) in the presence of Ag2CO3 (3 equiv) in the solvent 5% DMSO-DMF and proceeds at temperatures of 80-120 degrees C with a wide range of arene carboxylates and alkenes as substrates. The process is proposed to proceed by an initial Ar-SE reaction involving ipso attack of an electrophilic Pd(II) intermediate on an arene carboxylate to form an arylpalladium(II) species with loss of carbon dioxide. This intermediate is then proposed to react with an olefinic substrate by steps common to the Heck coupling process. Reoxidation of the liberated Pd(0) in situ is proposed to establish the catalytic cycle.
• Examining the Scope of Deriving β-Aryl Enones from Enol Silanes as Ketone Equivalents <i>via</i> Pd(II)-Mediated Sequential Dehydrosilylation and Arylation
  作者：Subba Rao Polimera、Andivelu Ilangovan、Murugaiah A. M. Subbaiah

  DOI：10.1021/acs.joc.3c00502

  日期：2023.6.2

  Silyl enol ethers were examined as a masked source of saturated ketones to derive β-aryl enones and their derivatives by dehydrosilylation to generate enones in situ and subsequent oxidative arylation with arylboronic acids as transmetallation coupling partners using relayed Pd(II) catalysis in one pot under base-free conditions. Oxygen was found to be an efficient and green oxidant to enable both

  将甲硅烷基烯醇醚作为饱和酮的掩蔽源进行检测，通过脱氢硅烷化原位生成烯酮，然后使用中继 Pd(II) 催化在一锅中进行原位氧化芳基化和芳基硼酸作为金属转移偶联伙伴，从而衍生出 β-芳基烯酮及其衍生物。无碱基条件。氧气被发现是一种有效的绿色氧化剂，可以实现烯醇硅烷的脱氢硅烷化和芳基化。此外，芳基化条件可以定制设计，以利用芳基卤化物作为芳基化剂的替代来源。通过 35 个实例（收率高达 95%）研究了制备范围，并且机理研究暗示了基于阳离子 Pd(II) 的催化体系。