methyl 4-cyclohexyl-3-methyl-4-oxobutanoate | 119924-84-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: methyl 4-cyclohexyl-3-methyl-4-oxobutanoate
• CAS: 119924-84-4
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: AROWCVNNTMIGIB-UHFFFAOYSA-N

物化性质

• 沸点：
  303.7±15.0 °C(Predicted)
• 密度：
  1.022±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 4-cyclohexyl-3-methyl-4-oxobutanoate 在 sodium hydroxide 、 二异丁基氢化铝 、 三氟乙酸 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 7.0h， 生成 cis-(RS,SR)-γ-cyclohexyl-γ-hydroxy-β-methylbutanoic acid lactone
  参考文献：
  名称：

  Stereoselective reduction of .gamma.-oxobutanoic acids using DIBAL-H and zinc chloride

  摘要：

  A variety of gamma-aromatic gamma-ketobutanoic acids can be reduced selectively, under optimized conditions, by the use of DIBAL-H and ZnCl2 to provide the (RS,SR)-gamma-aryl-gamma-hydroxy-beta-methylbutanoic acids. Further evidence has been gathered to support the hypothesis that the reaction proceeds by formation of a seven-membered ring complex with the aluminium or zinc atom bridging the ketone and carboxyl groups which preceeds the reduction step and that this templated reduction accounts for observed high diastereoselectivity. Also we have shown that some gamma-aryl-gamma-butyrolactones can be easily transformed via an oxidative cleavage of the aromatic ring to provide selective synthesis of either cis- or trans-tetrahydro-3-methyl-5-oxo-2-furancarboxylic acid derivatives.

  DOI：

  10.1021/jo00009a030
• 作为产物：
  描述：

  1-环己基-1-丙醇 在 Celite 、 双(三甲基硅烷基)氨基钾 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 methyl 4-cyclohexyl-3-methyl-4-oxobutanoate
  参考文献：
  名称：

  Stereoselective reduction of .gamma.-oxobutanoic acids using DIBAL-H and zinc chloride

  摘要：

  A variety of gamma-aromatic gamma-ketobutanoic acids can be reduced selectively, under optimized conditions, by the use of DIBAL-H and ZnCl2 to provide the (RS,SR)-gamma-aryl-gamma-hydroxy-beta-methylbutanoic acids. Further evidence has been gathered to support the hypothesis that the reaction proceeds by formation of a seven-membered ring complex with the aluminium or zinc atom bridging the ketone and carboxyl groups which preceeds the reduction step and that this templated reduction accounts for observed high diastereoselectivity. Also we have shown that some gamma-aryl-gamma-butyrolactones can be easily transformed via an oxidative cleavage of the aromatic ring to provide selective synthesis of either cis- or trans-tetrahydro-3-methyl-5-oxo-2-furancarboxylic acid derivatives.

  DOI：

  10.1021/jo00009a030

文献信息

• Atom-Economical Synthesis of Unsymmetrical Ketones through Photocatalyzed CH Activation of Alkanes and Coupling with CO and Electrophilic Alkenes
  作者：Ilhyong Ryu、Akihiro Tani、Takahide Fukuyama、Davide Ravelli、Maurizio Fagnoni、Angelo Albini

  DOI：10.1002/anie.201004854

  日期：2011.2.18

  A three‐component coupling between alkanes, CO, and electron‐deficient alkenes in the presence of a catalytic amount of (nBu4N)4W10O32 (TBADT) has resulted in the efficient formation of unsymmetrical ketones. This process is based on the carbonylation of alkyl radicals photocatalytically generated by CH activation of alkanes and the subsequent addition to alkenes (see scheme; EWG=electron‐withdrawing

  在催化量为（n Bu 4 N）4 W 10 O 32（TBADT）的存在下，烷烃，CO和缺电子烯烃之间的三组分偶联导致有效形成不对称酮。此过程基于烷烃的CH活化光催化产生的烷基的羰基化反应，随后将其添加到烯烃中（请参见方案； EWG =吸电子基团）。
• Carbonylation of Alkyl Radicals Derived from Organosilicates through Visible‐Light Photoredox Catalysis
  作者：Alex Cartier、Etienne Levernier、Vincent Corcé、Takahide Fukuyama、Anne‐Lise Dhimane、Cyril Ollivier、Ilhyong Ryu、Louis Fensterbank

  DOI：10.1002/anie.201811858

  日期：2019.2.4

  Primary, secondary, and tertiary alkyl radicals formed by the photocatalyzed oxidation of organosilicates underwent efficient carbonylation with carbon monoxide (CO) to give a variety of unsymmetrical ketones. This study introduces the possibility of radical carbonylation under a photooxidative regime.

  由有机硅酸盐的光催化氧化形成的伯，仲和叔烷基经过一氧化碳（CO）的有效羰基化反应，得到各种不对称酮。这项研究介绍了在光氧化条件下自由基羰基化的可能性。
• Metal-Free CH Bond Activation of Branched Aldehydes with a Hypervalent Iodine(III) Catalyst under Visible-Light Photolysis: Successful Trapping with Electron-Deficient Olefins
  作者：Shin A. Moteki、Asuka Usui、Sermadurai Selvakumar、Tiexin Zhang、Keiji Maruoka

  DOI：10.1002/anie.201406513

  日期：2014.10.6

  of a hypervalent iodine(III) catalyst under visible light photolysis allows a mild way of generating acyl radicals from various branched aldehydes, thereby giving the corresponding hydroacylated products almost exclusively. Another characteristic feature of this approach is the catalytic use of hypervalent iodine(III) reagent, which is a rare example on the generation of radicals in hypervalent iodine

  线性醛（RCH 2‐CHO）以及随后用缺电子的烯烃进行的加氢酰化反应可通过各种类型的金属和非金属催化剂/试剂进行。然而，与之形成鲜明对比的是，由于支化醛通过酰基自由基的容易的脱羰作用产生烷基的强烈趋势，迄今为止，尚未成功使用支链醛的报道。在此，在可见光光解下使用高价碘（III）催化剂可以采用温和的方式从各种支链醛生成酰基自由基，从而几乎完全提供相应的加氢酰化产物。这种方法的另一个特征是催化使用高价碘（III）试剂，这是在高价碘化学中生成自由基的罕见例子。
• Acyl radicals: intermolecular and intramolecular alkene addition reactions
  作者：Dale L. Boger、Robert J. Mathvink

  DOI：10.1021/jo00031a021

  日期：1992.2

  A full study of the use of phenyl selenoesters as precursors to acyl radicals and their subsequent participation in intermolecular and intramolecular alkene addition reactions is detailed. Primary alkyl-, vinyl-, and aryl-substituted acyl radicals generated by Bu3SnH treatment of the corresponding phenyl selenoesters participate cleanly in intermolecular addition reactions with alkenes bearing electron-withdrawing or radical-stabilizing substituents at rates that exceed those of the potentially competitive decarbonylation or reduction. Similarly, their intramolecular addition to activated or unactivated alkenes proceeds without significant competitive reduction or decarbonylation and at rates generally greater-than-or-equal-to 1 x 10(6) s-1 with some occurring at rates greater-than-or-equal-to 3 x 10(7) s-1. Consistent with their behavior in intermolecular addition reactions, the 5-exo-trig cyclizations of secondary and tertiary alkyl-substituted acyl radicals to an unactivated olefin acceptor may be accompanied by varying degrees of decarbonylation, even under low-temperature free-radical reaction conditions. Studies are presented which suggest that the intramolecular additions of acyl radicals to alkenes under the conditions detailed herein may be regarded as irreversible, kinetically controlled processes which exhibit regioselectivity that is predictable based on well-established empirical rules set forth for the analogous free-radical cyclization reactions of alkyl radicals.
• Phenyl selenoesters as effective precursors of acyl radicals for use in intermolecular alkene addition reactions
  作者：Dale L. Boger、R. J. Mathvink

  DOI：10.1021/jo00269a001

  日期：1989.4