4-methylhexa-1,4,5-trien-3-one | 1126624-03-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methylhexa-1,4,5-trien-3-one
• CAS: 1126624-03-0
• 化学式: C₇H₈O
• 分子量: 108.14
• InChiKey: CCRDCEUTJGMTMJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  4-methylhexa-1,4,5-trien-3-one 在 indium (III) iodide 作用下， 以 二氯甲烷 为溶剂， 以34%的产率得到3-(iodomethyl)-2-methylcyclopent-2-enone
  参考文献：
  名称：

  Formation of halogenated cyclopent-2-enone derivatives by interrupted Nazarov cyclizations

  摘要：

  Allenyl vinyl ketones were exposed to titanium and indium halides in order to carry out Nazarov cyclizations. Whereas Til(4) and InX3 (X = Cl, Br, and I) led to cyclopentenones in which a halogen was trapped highly regioselectively, the reactions mediated by TiBr4 gave mixtures of brominated isomers. When the allenyl vinyl ketones were treated first with Br-2 and then with TiBr4, doubly brominated cyclopentenones resulted, and treatment with I-2 followed by TFA gave cyclopentenones bearing both hydroxyl and iodo groups. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.10.052
• 作为产物：
  描述：

  4-methylhexa-1,4,5-trien-3-ol 在 manganese(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以37%的产率得到4-methylhexa-1,4,5-trien-3-one
  参考文献：
  名称：

  Synthesis of 5-Hydroxycyclopent-2-enones from Allenyl Vinyl Ketones via an Interrupted Nazarov Cyclization

  摘要：

  Treatment of an allenyl vinyl ketone with trifluoroacetic acid leads to Nazarov cyclization, and the intermediate carbocation is trapped efficiently by trifluoroacetate. Hydrolysis of the ester with methanol and basic alumina provides, in good to excellent overall yield, a 5-hydroxycyclopent-2-enone in which the alcohol is predominantly trans to a substituent at C-4.

  DOI：

  10.1021/ol900029d

文献信息

• Nazarov Cyclizations of an Allenyl Vinyl Ketone with Interception of the Oxyallyl Cation Intermediate for the Formation of Carbon−Carbon Bonds
  作者：Vanessa M. Marx、D. Jean Burnell

  DOI：10.1021/ja909073r

  日期：2010.2.10

  substitution on the diene. Cyclic dienes react with the oxyallyl cation by forming only one carbon-carbon bond, but the site of bond formation can be affected by steric hindrance. Electron-rich alkenes intercept the allyl cation by forming one carbon-carbon bond, or two carbon-carbon bonds through [3 + 2] cyclization. In some instances, further treatment of the initial products with BF(3) x Et(2)O leads

  用 BF(3) x Et(2)O 处理丙二烯基乙烯基酮会通过 Nazarov 反应生成环状氧烯丙基阳离子，当该反应在无环二烯存在下进行时，[4 + 3] 和 [3] + 2] 产品以高区域和立体选择性有效获得。[4 + 3] 与 [3 + 2] 产物的比例取决于二烯上的取代。环状二烯通过仅形成一个碳-碳键与氧烯丙基阳离子反应，但键形成的位置会受到空间位阻的影响。富电子烯烃通过[3+2]环化形成一个碳-碳键或两个碳-碳键来拦截烯丙基阳离子。在某些情况下，用 BF(3) x Et(2)O 进一步处理初始产品会导致平衡产品的产量良好。
• Trapping the Oxyallyl Cation Intermediate Derived from the Nazarov Cyclization of Allenyl Vinyl Ketones with Nitrogen Heterocycles
  作者：Vanessa M. Marx、François M. LeFort、D. Jean Burnell

  DOI：10.1002/adsc.201000722

  日期：2011.1.10

  intermediate of the Lewis acid‐initiated Nazarov cyclization of an allenyl vinyl ketone (AVK) was trapped by pyrroles and indoles. The yields ranged from modest to high (up to 93%), and in both cases, only two of the three possible products were produced. Cyclopent‐2‐enones substituted at the 5‐position were predominantly produced, however with increasing alkyl substitution or placement of an electron‐withdrawing

  路易斯酸引发的烯丙基乙烯基酮（AVK）的Nazarov环化的阳离子中间体被吡咯和吲哚捕获。产量从中等到高（高达93％）不等，在两种情况下，只生产了三种可能产品中的两种。主要产生在5位取代的环戊2-烯酮，但是随着烷基取代的增加或氮上吸电子基团的放置，还可能形成替代的区域异构体。这项研究的结果表明，在电子上优选的位置是相对于氧烯丙基阳离子的氧的位置α，而对于更立体地阻碍反应的配偶体则优选环外位置。
• Synthesis of 5-Hydroxycyclopent-2-enones from Allenyl Vinyl Ketones via an Interrupted Nazarov Cyclization
  作者：Vanessa M. Marx、D. Jean Burnell

  DOI：10.1021/ol900029d

  日期：2009.3.19

  Treatment of an allenyl vinyl ketone with trifluoroacetic acid leads to Nazarov cyclization, and the intermediate carbocation is trapped efficiently by trifluoroacetate. Hydrolysis of the ester with methanol and basic alumina provides, in good to excellent overall yield, a 5-hydroxycyclopent-2-enone in which the alcohol is predominantly trans to a substituent at C-4.
• Formation of halogenated cyclopent-2-enone derivatives by interrupted Nazarov cyclizations
  作者：Vanessa M. Marx、T. Stanley Cameron、D. Jean Burnell

  DOI：10.1016/j.tetlet.2009.10.052

  日期：2009.12

  Allenyl vinyl ketones were exposed to titanium and indium halides in order to carry out Nazarov cyclizations. Whereas Til(4) and InX3 (X = Cl, Br, and I) led to cyclopentenones in which a halogen was trapped highly regioselectively, the reactions mediated by TiBr4 gave mixtures of brominated isomers. When the allenyl vinyl ketones were treated first with Br-2 and then with TiBr4, doubly brominated cyclopentenones resulted, and treatment with I-2 followed by TFA gave cyclopentenones bearing both hydroxyl and iodo groups. (C) 2009 Elsevier Ltd. All rights reserved.