6,6-dimethyl-1-phenyl-3-heptanone

• 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: 6,6-dimethyl-1-phenyl-3-heptanone
• 英文别名: 6,6-dimethyl-1-phenylheptan-3-one
• 化学式: C₁₅H₂₂O
• 分子量: 218.339
• InChiKey: QHDQIRNEKLAYEK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  3,3-二甲基-1-丁烯 在 十二羰基三钌 盐酸 作用下， 以 甲苯 为溶剂， 反应 6.0h， 生成 6,6-dimethyl-1-phenyl-3-heptanone
  参考文献：
  名称：

  Catalytic Activation of C−H and C−C Bonds of Allylamines via Olefin Isomerization by Transition Metal Complexes

  摘要：

  The metal-catalyzed reaction of olefins with allylamines bearing coordination sites (2-pyridyl groups) was studied. With Ru-3(CO)(12) as catalyst, activation of C-H bonds led to the formation of ketimines that were hydrolyzed to give asymmetric ketones. With [(C8H14)(2)RhCl](2), both C-H and C-C bonds were activated and symmetric ketones were formed on hydrolysis. The reaction involves double bond migration of the allylamine to form an aldimine.

  DOI：

  10.1021/ol990357b

文献信息

• Tandem Catalytic Triple-Bond Cleavage of Alkyne in Association with Aldehyde, Alkene, and Water
  作者：Chul-Ho Jun、Kyung-Mi Cha、Eun-Ae Jo

  DOI：10.1055/s-0029-1218000

  日期：2009.11

  In this tandem reaction the carbon-carbon triple bond of an alkyne is catalytically cleaved in association with aldehyde, al­kene, and H2O under catalyst mixtures of Rh(I), 2-amino-3-picoline, primary amine, and acid. The reaction starts with chelation-assisted hydroacylation of the alkyne with an aldehyde. The retro-Mannich-type fragmentation of the resulting α,β-unsaturated ketimine by an amine and acid affords a ketimine and an aldimine, which is trapped by an alkene and give ketones after hydrolysis.

  在这个串联反应中，炔烃的碳碳三键在铑(I)、2-氨基-3-吡啶、一级胺和酸的催化混合物的作用下，与醛、烯烃和水共同催化断裂。反应以炔烃与醛的螯合辅助羟基醇化开始。生成的α,β-不饱和酮亚胺经过胺和酸的逆曼尼希类裂解，产生酮亚胺和醛亚胺，后者被烯烃捕获，经过水解生成酮。
• Ti-Catalyzed Modular Ketone Synthesis from Carboxylic Derivatives and <i>gem</i>-Dihaloalkanes
  作者：Jiabin Ni、Xiaowen Xia、Danyu Gu、Zhaobin Wang

  DOI：10.1021/jacs.3c04009

  日期：2023.7.12

  Ketones are ubiquitous in organic synthesis. However, the general method to convert widely available carboxylic acids, unactivated esters, and amides into ketones remains elusive. Herein, we describe the Ti-catalyzed modular ketone synthesis from carboxylic derivatives and easily accessed gem-dihaloalkanes. Notably, this protocol could achieve the direct catalytic olefination of carboxylic acids. This

  酮在有机合成中普遍存在。然而，将广泛使用的羧酸、未活化的酯和酰胺转化为酮的一般方法仍然难以捉摸。在此，我们描述了由羧酸衍生物和易于获得的宝石二卤代烷烃进行钛催化的模块化酮合成。值得注意的是，该方案可以实现羧酸的直接催化烯化。该方法具有一系列的烯化和亲电转化以及良好的官能团相容性，可以快速获得各种官能化酮。初步的机理研究提供了对反应途径的深入了解，并支持亚烷基二茂钛和宝石双金属配合物的中间作用。
• C−H and C−C Bond Activation of Primary Amines through Dehydrogenation and Transimination
  作者：Chul-Ho Jun、Kwan-Yong Chung、Jun-Bae Hong

  DOI：10.1021/ol015563+

  日期：2001.3.1

  [GRAPHICS]Dehydrogenation and subsequent transimination of primary amines offer a new pathway for C-H bond activation, ortho-alkylation, and C-C bond activation to afford a variety of ketones in the reaction of l-alkene by a cocatalyt system of Rh(I) and 2-amino-3-picoline.
• The effects of amine and acid catalysts on efficient chelation-assisted hydroacylation of alkene with aliphatic aldehyde
  作者：Eun-Ae Jo、Chul-Ho Jun

  DOI：10.1016/j.tetlet.2009.02.091

  日期：2009.7

  Efficient intermolecular hydroacylation of 1-alkene with aliphatic aldehyde was achieved using a catalyst mixture of cyclohexylamine, p-trifluoromethylbenzoic acid, Wilkinson's complex and 2-amino-3-picoline. The formation of unwanted aldol side-product was avoided through the conjugate addition of cyclohexylamine to the aldol intermediate that was initially generated, followed by the retro-Mannich-type fragmentation of the resulting beta-aminoaldimine.
• Catalytic Activation of C−H and C−C Bonds of Allylamines via Olefin Isomerization by Transition Metal Complexes
  作者：Chul-Ho Jun、Hyuk Lee、Jae-Bum Park、Dae-Yon Lee

  DOI：10.1021/ol990357b

  日期：1999.12.1

  The metal-catalyzed reaction of olefins with allylamines bearing coordination sites (2-pyridyl groups) was studied. With Ru-3(CO)(12) as catalyst, activation of C-H bonds led to the formation of ketimines that were hydrolyzed to give asymmetric ketones. With [(C8H14)(2)RhCl](2), both C-H and C-C bonds were activated and symmetric ketones were formed on hydrolysis. The reaction involves double bond migration of the allylamine to form an aldimine.