1-methyl-2-oxocyclohexane-1-carbaldehyde | 37709-42-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-methyl-2-oxocyclohexane-1-carbaldehyde
• 英文别名: 1-Methyl-2-oxo-cyclohexanecarbaldehyde；1-methyl-2-oxocyclohexanecarbaldehyde；2-formyl-2-methylcyclohexanone；1-Methyl-2-oxo-cyclohexancarbaldehyd
• CAS: 37709-42-5
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: NGOXDDFBXWVZEY-UHFFFAOYSA-N

物化性质

• 沸点：
  115-120 °C(Press: 50 Torr)
• 密度：
  1.095±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  1-methyl-2-oxocyclohexane-1-carbaldehyde 在 正丁基锂 作用下， 以 苯 为溶剂， 反应 15.0h， 生成 (E)-4-(2-Ethynyl-2-hydroxy-1-methyl-cyclohexyl)-but-3-en-2-one
  参考文献：
  名称：

  Studies in base-catalyzed allenic oxy-Cope rearrangement: an expedient synthesis of functionalized bicyclo[4.3.0] and -[4.4.0] systems and 3,5-cycloundecadien-1-one

  摘要：

  The base-catalyzed oxy-Cope rearrangement of systems incorporating an allenic pi system was studied. The rearrangement incidentally leads to functionalized bicyclo[4.3.0]nonane 15, bicyclo[4.4.0]decanes 6 and 10, and 3,5-cycloundecadien-1-one 20. The effect of ring size and nature of the base on the rearrangement was also studied.

  DOI：

  10.1021/jo00072a035
• 作为产物：
  描述：

  Cyclohexanone-2-carbaldehyde 在 sodium 、 苯 作用下， 生成 1-methyl-2-oxocyclohexane-1-carbaldehyde
  参考文献：
  名称：

  263.合成桑顿宁的实验。第二部分 桑托宁中含有二烯酮体系的化合物的制备

  摘要：

  DOI：

  10.1039/jr9520001437

文献信息

• Exploiting Carbonyl Groups to Control Intermolecular Rhodium-Catalyzed Alkene and Alkyne Hydroacylation
  作者：Thomas J. Coxon、Maitane Fernández、James Barwick-Silk、Alasdair I. McKay、Louisa E. Britton、Andrew S. Weller、Michael C. Willis

  DOI：10.1021/jacs.7b05713

  日期：2017.7.26

  Rh-catalyzed intermolecular alkene and alkyne hydroacylation reactions. By using cationic rhodium catalysts incorporating bisphosphine ligands, efficient and selective reactions are achieved for β-amido, β-ester, and β-keto aldehyde substrates, providing a range of synthetically useful 1,3-dicarbonyl products in excellent yields. A correspondingly broad selection of alkenes and alkynes can be employed

  容易获得的 β-羰基取代的醛被证明是 Rh 催化的分子间烯烃和炔烃加氢酰化反应的特殊底物。通过使用掺入双膦配体的阳离子铑催化剂，β-酰胺基、β-酯和β-酮醛底物实现了高效和选择性的反应，以优异的产率提供了一系列合成有用的1,3-二羰基产物。可以使用相应广泛的烯烃和炔烃选择。对于炔底物，使用包含 Ampaphos 配体的催化剂会触发区域选择性转换，从而可以高效地以高选择性制备直链和支链异构体。提供了结构数据、确认醛螯合和建议的机制。
• Asymmetric Synthesis and in vivo Biological Inactivity of the Right-Hand Terpenoid Fragment of Terpendole E
  作者：Masato Oikawa、Ryo Hashimoto、Makoto Sasaki

  DOI：10.1002/ejoc.201001104

  日期：2011.1

  Synthesis of the DEF-ring terpenoid fragment of terpendole E, an Eg5 inhibitor, is described. The DE-ring was constructed by a modification of Barrero's radical cyclization. The F-ring tetrahydropyran was then constructed by acid-induced cyclization of an epoxy alcohol, which was prepared by cross-metathesis followed by Shi's epoxidation. Cell-based assays indicated that the DEF-ring fragment is not

  描述了 Eg5 抑制剂 terpendole E 的 DEF 环萜类片段的合成。DE-环是通过对 Barrero 自由基环化的修饰而构建的。然后通过环氧醇的酸诱导环化构建 F 环四氢吡喃，环氧醇通过交叉复分解和 Shi 环氧化制备。基于细胞的测定表明DEF-环片段不能抑制人癌细胞系的细胞生长和细胞周期进程，表明单独的DEF-环片段不足以实现生物活性。
• New Strategy for Forging Contiguous Quaternary Carbon Centers via H2O2-Mediated Ring Contraction
  作者：Weiqing Xie、Jiadong Hu、Xin Yu

  DOI：10.1055/s-0036-1590979

  日期：2017.12

  product synthesis. A general protocol that enables stereospecific construction of all stereoisomers of such a moiety remains elusive. In this article, we will discuss the oxidative ring contraction of all-substituted cyclic α-formyl ketones mediated by H2O2, which provides a facile access to the stereospecific construction of contiguous quaternary carbon centers.

  连续四元碳中心的立体有择构建构成了天然产物合成的主要挑战。使这种部分的所有立体异构体的立体特异性构建成为可能的通用协议仍然难以捉摸。在本文中，我们将讨论由 H2O2 介导的全取代环状 α-甲酰基酮的氧化环收缩，这为连续季碳中心的立体有择构建提供了便利。
• Stereospecific Construction of Contiguous Quaternary All-Carbon Centers by Oxidative Ring Contraction
  作者：Xin Yu、Jiadong Hu、Zhigao Shen、Hui Zhang、Jin-Ming Gao、Weiqing Xie

  DOI：10.1002/anie.201609975

  日期：2017.1.2

  ketones was facilitated by the action of H2O2 under operationally simple and environmentally benign reaction conditions. The process was highly regioselective and enables stereospecific construction of contiguous quaternary all‐carbon centers from stereodefined all‐substituted all‐cyclic ketones. The asymmetric syntheses of (+)‐cuparene and (+)‐tochuinyl acetate were also successively achieved by taking advantage

  在操作简单和环境友好的反应条件下，H 2 O 2的作用促进了环状α-甲酰基酮的氧化环收缩。该过程具有高度的区域选择性，并能够从立体定义的全取代的全环酮立体构筑连续的季碳全碳中心。利用该新方案还成功实现了（+）-cuparene和（+）-tochuinyl乙酸酯的不对称合成。
• Relay ring-closing metathesis strategies towards the synthesis of the ABC tricycle of Taxol
  作者：Andrea Ojeda-Porras、Rémi Aouzal、Claire Wilson、Joëlle Prunet

  DOI：10.1016/j.tet.2022.132630

  日期：2022.1

  tricycle of Taxol are presented. They both involve a relay ring-closing metathesis reaction to make the central B ring in a convergent fashion. In the first approach, the extender arm is positioned on the A ring, and the C ring bears the relay tether in the second route. Metathesis precursors with diverse extender arms were efficiently synthesised; unfortunately, the crucial metathesis reactions failed

  介绍了两种合成紫杉醇 ABC 三轮车的路线。它们都涉及中继闭环复分解反应，以使中央 B 环以收敛的方式。在第一种方法中，延长臂位于 A 环上，而 C 环在第二种路线中承载中继系绳。高效合成了具有多种扩展臂的复分解前体；不幸的是，关键的复分解反应在所有情况下都未能提供目标化合物。