5-methyl-1,7-diphenyl-3-heptanone

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 5-methyl-1,7-diphenyl-3-heptanone
• 英文别名: 5-methyl-1,7-diphenylheptan-3-one
• 化学式: C₂₀H₂₄O
• 分子量: 280.41
• InChiKey: MWRWHCDYQDUINK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 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：

  4-苯基-2-丁醇 在 Ru-MACHO 、 potassium tert-butylate 作用下， 以 甲苯 为溶剂， 以72 %的产率得到5-methyl-1,7-diphenyl-3-heptanone
  参考文献：
  名称：

  钌催化仲醇的自偶联

  摘要：

  报道了一种简单的仲醇自偶联催化方法，从而在温和条件下合成β-支化酮。明确的钌钳形络合物催化了该反应。优化研究表明叔丁醇钠是这种转化的合适碱。官能化芳基甲醇、杂芳基甲醇以及直链和支链脂肪族仲醇容易发生催化自偶联反应。机理研究表明，催化剂和碱对于实现仲醇脱氢为酮、随后的受控羟醛缩合以及α,β-不饱和中间体的进一步加氢，从而选择性形成β-支化酮产物至关重要。值得注意的是，非无辜的 PNP 配体在催化剂中表现出胺-酰胺金属-配体合作，在促进仲醇的催化自偶联方面发挥了关键作用。释放的分子氢和水是唯一的副产品。

  DOI：

  10.1021/acs.joc.3c02029

文献信息

• Reaction of α,β-unsaturated imidates with Grignard reagents leading to 2-alkyl 1,3-diimines
  作者：Seiichi Inoue、Osamu Suzuki、Kikumasa Sato

  DOI：10.1039/c39850001773

  日期：——

  Methyl N-phenylacrylimidate (1a) reacted with alkyl- and aryl-magnesium bromides in ether at 0 °C to give 2-alkyl 1,3-diketones (3a) in a good yield after aqueous work-up; methyl N-phenylcrotonimidate (1b) and N-phenylcinnamimidate (1c) with alkylmagnesium bromides furnished analogous 1,3-diketones (3) as the major products after hydrolysis of the corresponding stable diimines (2).

  N-苯基丙烯酰亚胺亚甲基（1a）与烷基溴和芳基溴化镁在乙醚中于0°C反应，经过水处理后，以良好的收率得到2-烷基1,3-二酮（3a）。甲基Ñ -phenylcrotonimidate（1B）和Ñ -phenylcinnamimidate（1C）与烷基镁溴化物布置类似的1,3-二酮类（3）与相应的稳定二亚胺（水解后的主要产物2）。
• Synthesis of 2-Alkyl-Substituted 1,3-Diketones via the 1,4-Addition of the Grignard Reagents to α,β-Unsaturated Imidates
  作者：Seiichi Inoue、Osamu Suzuki、Kikumasa Sato

  DOI：10.1246/bcsj.62.1601

  日期：1989.5

  formed by the reaction of methyl N-phenylacrylimidate with ethylmagnesium bromide in 80% yield. Similar diketones were obtained from methyl N-phenylcrotonimidate and N-phenylcinnamimidate with the Grignard reagents. The coupling of N-magnesio α-methoxy enamine and ketenimine, both of which are formed through the initial 1,4-addition of the Grignard reagent to α,β-unsaturated imidate, is the most plausible

  4-丙基-3,5-壬二酮通过N-苯基丙烯酰亚胺甲酯与溴化乙基镁的反应选择性地形成，产率为80%。用格氏试剂从 N-苯基巴豆酰亚胺甲酯和 N-苯基肉桂酰亚胺酯得到类似的二酮。N-氧化镁α-甲氧基烯胺和烯酮亚胺的偶联是形成二酮的最合理途径，两者都是通过格氏试剂与α,β-不饱和亚胺酸酯的初始1,4-加成形成的。
• Ruthenium-Catalyzed Self-Coupling of Primary and Secondary Alcohols with the Liberation of Dihydrogen
  作者：Ilya S. Makarov、Robert Madsen

  DOI：10.1021/jo4008699

  日期：2013.7.5

  The dehydrogenative self-condensation of primary and secondary alcohols has been studied in the presence of RuCl2(IiPr)(p-cymene). The conversion of primary alcohols into esters has been further optimized by using magnesium nitride as an additive, which allows the reaction to take place at a temperature and catalyst loading lower than those described previously. Secondary alcohols were dimerized into racemic ketones by a dehydrogenative Guerbet reaction with potassium hydroxide as the additive. The transformation gave good yields of the ketone diners with a range of alkan-2-ols, whereas more substituted secondary alcohols were unreactive. The reaction proceeds by dehydrogenation to the ketone, followed by an aldol reaction and hydrogenation of the resulting enone.