2-Methyl-5-acetylcyclohexanon | 49576-28-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Methyl-5-acetylcyclohexanon
• 英文别名: 5-acetyl-2-methyl-cyclohexanone；2-Methyl-5-acetyl-cyclohexan-1-one；5-acetyl-2-methylcyclohexan-1-one
• CAS: 49576-28-5；50795-93-2；87099-97-6；56893-77-7
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: HQMKNFNWDDKHPJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-Methyl-5-acetylcyclohexanon 、 三甲基硅烷化重氮甲烷 在 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 2.5h， 以51%的产率得到
  参考文献：
  名称：

  Selectivity Control in Alkylidene Carbene-Mediated C−H Insertion and Allene Formation

  摘要：

  Regioselectivity of alkylidene carbene-mediated C-H insertion was explored utilizing electronic, conformational, steric, and stereoelectronic effects. Relying on these factors, highly regio- and chemoselective carbene insertion reaction of C-H bonds in different environments could be obtained. The observed selectivity clearly indicates that an electronic effect plays a more important role than steric effect. In general, C-H bonds in conformationally rigid cyclic environments are less reactive than those in acyclic systems toward carbene insertion, and in this situation, a competing intermolecular reaction between alkylidene carbene and trimethylsilyldiazomethane led to the formation of allenylsilanes. The formation of allenylsilane becomes more favorable as the concentration of reaction becomes higher, as well as the C-H bonds undergoing insertion becomes electronically and conformationally deactivated.

  DOI：

  10.1021/jo102180f
• 作为产物：
  描述：

  (1R)-trans-Isoketopinic acid 在 盐酸 、 sodium hydroxide 、 氯化亚砜 、 sodium azide 、 苯 作用下， 生成 2-Methyl-5-acetylcyclohexanon
  参考文献：
  名称：

  Ishidate; Tani, Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1942, vol. 62, p. 12,14; dtsch. Ref. S. 8

  摘要：

  DOI：

文献信息

• The mechanistic study and synthetic applications of the base treatment in the ozonolytic reactions
  作者：Yung-Son Hon、Sheng-Wun Lin、Ling Lu、Yao-Jung Chen

  DOI：10.1016/0040-4020(95)98699-i

  日期：1995.4

  E1cb mechanism is the overwhelming process in the reaction of bases and ozonides. As a quenching agent in the ozonolysis of a variety of alkenes, the reactions involving triethylamine often gave better yields and proceeded faster than those involving methyl sulfide. On the other hand, in the presence of 4 Å molecular sieves, the secondary amines reacted with mono- and 1,1-di-substituted ozonides to afford

  E1cb机制是碱和臭氧化物反应中的压倒性过程。作为各种烯烃的臭氧分解反应的淬灭剂，涉及三乙胺的反应通常比涉及甲基硫醚的反应收率更高，并且进行速度更快。另一方面，在4Å分子筛的存在下，仲胺与单和1,1-二取代的臭氧化物反应，以高收率提供还原性胺化产物。反应混合物中甲酸铵的形成也支持了臭氧化物与胺反应中的E1cb机理。
• Pyridine Is an Organocatalyst for the Reductive Ozonolysis of Alkenes
  作者：Rachel Willand-Charnley、Thomas J. Fisher、Bradley M. Johnson、Patrick H. Dussault

  DOI：10.1021/ol300617r

  日期：2012.5.4

  Whereas the cleavage of alkenes by ozone typically generates peroxide intermediates that must be decomposed in an accompanying step, ozonolysis in the presence of pyridine directly generates ketones or aldehydes through a process that neither consumes pyridine nor generates any detectable peroxides. The reaction is hypothesized to involve nucleophile-promoted fragmentation of carbonyl oxides via formation

  尽管通过臭氧裂解烯烃通常会产生必须在后续步骤中分解的过氧化物中间体，但在吡啶存在下的臭氧分解通过既不消耗吡啶也不产生任何可检测过氧化物的过程直接产生酮或醛。假设该反应涉及通过形成两性离子过氧缩醛，亲核试剂促进羰基氧化物的断裂。
• Complementary Catalytic Strategies to Access ?-Chiral Aldehydes
  作者：Clément Mazet

  DOI：10.2533/chimia.2013.658

  日期：——

  The present article summarizes the development of two novel and complementary catalytic methods to access ?-chiral aldehydes. A C1-symmetric chiral (P,N) ligand with a structure derived from the ubiquitous binepine scaffold has been specifically designed for the Pd-catalyzed ?-arylation of aldehydes to access indane derivatives with a well-defined quaternary stereocenter in high yields and excellent enantioselectivities. In addition, a dinuclear palladium hydride catalyst has been synthesized for the isomerization of terminal and trisubstituted epoxides into aldehydes and ketones respectively. Combined experimental and theoretical investigations pointed to an unprecedented 'epoxide-opening/hydride-transfer' sequence. The mechanism also features two distinct enantio-determining steps in the kinetic resolution of racemic epoxides.

  本文总结了两种新颖且互补的催化方法的发展，用于获取α-手性醛类化合物。一种源自广泛存在的bipine桥架的C1对称手性（P,N）配体已经专门设计用于Pd催化的α-芳基化反应，以获得具有明确定义的四元手性中心的茚烷衍生物，产率高且选择性优异。此外，合成了一种双核钯氢化物催化剂，用于将末端和三取代环氧化物异构化为相应的醛和酮。结合实验和理论研究指出了一种前所未有的“环氧化物开环/氢转移”序列。该机制还包括在消旋环氧化物的动力学拆分过程中的两个不同的手性决定步骤。
• ‘Reductive ozonolysis’ via a new fragmentation of carbonyl oxides
  作者：Chris Schwartz、Joseph Raible、Kyle Mott、Patrick H. Dussault

  DOI：10.1016/j.tet.2006.08.092

  日期：2006.11

  This account describes the development of methodologies for ‘reductive’ ozonolysis, the direct ozonolytic conversion of alkenes into carbonyl groups without the intermediacy of 1,2,4-trioxolanes (ozonides). Ozonolysis of alkenes in the presence of DMSO produces a mixture of aldehyde and ozonide. The combination of DMSO and Et3N results in improved yields of carbonyls but still leaves unacceptable levels

  该文献描述了“还原”臭氧分解方法的发展，即烯烃直接臭氧分解转化为羰基而没有1,2,4-三氧杂环戊烷（臭氧化物）的中介作用。在DMSO存在下烯烃的臭氧分解产生醛和臭氧化物的混合物。DMSO和Et 3 N的组合可提高羰基化合物的收率，但仍然留下不可接受的残留臭氧化物。在不存在DMSO的情况下，使用仲胺或叔胺可获得类似的结果。据认为，胺的影响是由转化成相应的N-氧化物引起的。胺N存在下的臭氧分解氧化物有效抑制臭氧化物的形成，产生高产率的醛。假设与胺氧化物的反应涉及空前的羰基氧化物捕集以产生两性离子加合物，该两性离子加合物断裂以产生所需的羰基，胺和1 O 2。
• Copper ‘ate’ complexes of α-ethoxyvinyl-lithium: reagents for coupling and 1,4 addition of a masked acyl anion
  作者：Robert K. Boeckman、Kenneth J. Bruza、J. E. Baldwin、O. W. Lever

  DOI：10.1039/c39750000519

  日期：——

  Stoicheiometric and mixed organocuprate reagents have been prepared from α-ethoxyvinyl-lithium and undergo ready conjugate addition and coupling reactions.

  由α-乙氧基乙烯基锂制备了化学计量的和混合的有机铜酸盐试剂，并进行了共轭加成和偶联反应。