3-(2-Methyl-1-propen-1-yl)cyclohexan-1-one | 29843-69-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(2-Methyl-1-propen-1-yl)cyclohexan-1-one
• 英文别名: 3-(2-methylpropen-1-yl)cyclohexanone；3-(2-Methyl-1-propenyl)cyclohexanone；3-(2-methylprop-1-enyl)cyclohexan-1-one
• CAS: 29843-69-4
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: AZSDTKJJMQIYSE-UHFFFAOYSA-N

物化性质

• 沸点：
  229.4±19.0 °C(Predicted)
• 密度：
  0.981±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(2-Methyl-1-propen-1-yl)cyclohexan-1-one 在 tris(dibenzoylmethano)iron(III) samarium diiodide 、 氢碘酸 、 四丁基碘化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 3-(2-Methyl-1-propen-3-yl)cyclohexanone
  参考文献：
  名称：

  A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction

  摘要：

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.

  DOI：

  10.1021/jo00013a008
• 作为产物：
  描述：

  (1R,3R)-3-(2-Methyl-propenyl)-cyclohexanol 在 chromium(VI) oxide 作用下， 以 吡啶 为溶剂， 反应 24.0h， 生成 3-(2-Methyl-1-propen-1-yl)cyclohexan-1-one
  参考文献：
  名称：

  Julia,M.; Descoins,C., Bulletin de la Societe Chimique de France, 1970, p. 1805 - 1815

  摘要：

  DOI：

文献信息

• Organo[2-(hydroxymethyl)phenyl]dimethylsilanes as Mild and Reproducible Agents for Rhodium-Catalyzed 1,4-Addition Reactions
  作者：Yoshiaki Nakao、Jinshui Chen、Hidekazu Imanaka、Tamejiro Hiyama、Yoshitaka Ichikawa、Wei-Liang Duan、Ryo Shintani、Tamio Hayashi

  DOI：10.1021/ja071969r

  日期：2007.7.1

  achievement of the corresponding enantioselective transformations using the tetraorganosilicon reagents, providing the silicon-based approach to optically active ketones and substituted piperidones that serve as synthetic intermediates of pharmaceuticals. A rhodium alkoxide species is suggested to be responsible for a transmetalation step on the basis of the observed kinetic resolution of a racemic chiral phenylsilane

  稳定且可重复使用的四有机硅试剂、烯基-、芳基-和甲硅烷基[2-(羟甲基)苯基]二甲基硅烷，在温和的铑催化下与 α,β-不饱和羰基受体发生 1,4-加成反应。该反应耐受多种官能团，适用于克级合成。手性二烯配体的使用允许使用四有机硅试剂实现相应的对映选择性转化，为用作药物合成中间体的光学活性酮和取代哌啶酮提供基于硅的方法。根据观察到的对映选择性 1 中的外消旋手性苯基硅烷的动力学分辨率，建议铑醇盐物种负责金属转移步骤，
• Organomanganese (II) reagents XVI1: copper-catalyzed 1,4-addition of organomanganese chlorides to conjugated enones
  作者：Gérard Cahiez、Mouad Alami

  DOI：10.1016/s0040-4039(00)99434-6

  日期：1989.1

  Copper-catalyzed conjugate addition of organomanganese chlorides to conjugated enones in THF, at 0°C, leads to the 1,4 addition products in high yields. The scope of the reaction is very large and the results are generally better than those obtained from organomagnesium compounds in the presence of a copper salt as well as from organocopper or cuprate reagents. Furthermore organomanganese chlorides are indisputably

  在0℃下，铜催化的有机锰氯化物在THF中的共轭烯酮的共轭加成反应，可高产率地产生1,4加成产物。该反应的范围非常大，其结果通常比在铜盐以及有机铜或铜酸盐试剂存在下从有机镁化合物获得的结果更好。此外，有机锰氯化物无疑比后者更便宜，更稳定。
• Organomanganese (II) reagents XI.
  作者：G. Cahiez、M. Alami

  DOI：10.1016/s0040-4039(00)84042-3

  日期：1986.1

  The reaction of organomanganese reagents such as RMnX, R2Mn, R3MnLi and R3MnMgX with cyclohexenone has been studied. Two major pathways have been observed : conjugate addition and β reductive dimerization. Similar results have been obtained with organomagnesium compounds in presence of a catalytic amount of manganous salts.

  研究了RMnX，R 2 Mn，R 3 MnLi和R 3 MnMgX等有机锰试剂与环己烯酮的反应。已经观察到两个主要途径：缀合物添加和β还原二聚化。在催化量的锰盐存在下，使用有机镁化合物也获得了相似的结果。
• CAHIEZ, GERARD;ALAMI, MOUAD, TETRAHEDRON LETT., 30,(1989) N7, C. 3541-3544
  作者：CAHIEZ, GERARD、ALAMI, MOUAD

  DOI：——

  日期：——
• A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction
  作者：Gary A. Molander、Jeffrey A. McKie

  DOI：10.1021/jo00013a008

  日期：1991.6

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.