4-Hydroxy-2,3,4-trimethyl-2-cyclobuten-1-one | 155190-76-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-Hydroxy-2,3,4-trimethyl-2-cyclobuten-1-one
• 英文别名: 4-hydroxy-2,3,4-trimethylcyclobut-2-enone；4-Hydroxy-2,3,4-trimethylcyclobut-2-en-1-one
• CAS: 155190-76-4
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: DWDFIMJWMLPBDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Hydroxy-2,3,4-trimethyl-2-cyclobuten-1-one 在 正丁基锂 、 四丁基氟化铵 、 potassium carbonate 、 silver(l) oxide 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 30.42h， 生成 1-(6-Hydroxy-1-hexynyl)-4-methoxy-2,3,4-trimethyl-2-cyclobuten-1-ol
  参考文献：
  名称：

  A method for the stereoselective construction of 4-alkoxy-5-alkylidenecyclopentenones by the tandem ring expansion-functionalization of 1-alkynylcyclobutenols using a palladium-mercury cocatalytic system

  摘要：

  1-(1-Alkynyl)-4-methoxy-4-methyl-2-cyclobutenols, prepared by nucleophilic functionalization of cyclobutenediones, were transformed with high stereoselectivity into 4-methoxy-4-methyl-5-alkylidenecyclopentenones. The action of stoichiometric Hg(OCOCF3)(2) and then metathesis with NaCl produced 5-(1-(chloromercurio)alkylidene)-4-methoxy-4-methyl-2-cyclopentenones which were stereospecifically functionalized by palladium-mediated allylation and hydroxybutenylation. Treatment with Br-2/DMSO led to stereospecific bromodemercuration. The 1-(1-alkynyl)-4-methoxy-4-methyl-2-cyclobutenols underwent efficient and very stereoselective tandem ring expansion-functionalizations in the presence of three different allylic chlorides and a catalyst system composed of 10% Hg(OCOCF3)(2) and 10% PdCl2. All products can be obtained with a stereoselectivity greater than 99:1 at the exocyclic alkene.

  DOI：

  10.1021/jo00084a038
• 作为产物：
  描述：

  甲基锂 、 3,4-dimethylcyclobut-3-ene-1,2-dione 以 四氢呋喃 、 乙醚 为溶剂， 反应 0.5h， 以78%的产率得到4-Hydroxy-2,3,4-trimethyl-2-cyclobuten-1-one
  参考文献：
  名称：

  A method for the stereoselective construction of 4-alkoxy-5-alkylidenecyclopentenones by the tandem ring expansion-functionalization of 1-alkynylcyclobutenols using a palladium-mercury cocatalytic system

  摘要：

  1-(1-Alkynyl)-4-methoxy-4-methyl-2-cyclobutenols, prepared by nucleophilic functionalization of cyclobutenediones, were transformed with high stereoselectivity into 4-methoxy-4-methyl-5-alkylidenecyclopentenones. The action of stoichiometric Hg(OCOCF3)(2) and then metathesis with NaCl produced 5-(1-(chloromercurio)alkylidene)-4-methoxy-4-methyl-2-cyclopentenones which were stereospecifically functionalized by palladium-mediated allylation and hydroxybutenylation. Treatment with Br-2/DMSO led to stereospecific bromodemercuration. The 1-(1-alkynyl)-4-methoxy-4-methyl-2-cyclobutenols underwent efficient and very stereoselective tandem ring expansion-functionalizations in the presence of three different allylic chlorides and a catalyst system composed of 10% Hg(OCOCF3)(2) and 10% PdCl2. All products can be obtained with a stereoselectivity greater than 99:1 at the exocyclic alkene.

  DOI：

  10.1021/jo00084a038

文献信息

• Stereocontrolled [4+1] Annulation of α-Hydroxycyclobutenones: Synthesis of Polysubstituted Cyclopentenones
  作者：Xu Mao、Peidong Song、Yu Hao、Zezhong Sun、Xiangdong Hu

  DOI：10.1002/adsc.201600670

  日期：2016.12.7

  A stereocontrolled [4+1] annulation of α‐hydroxycyclobutenones has been disclosed. For the first time, α‐hydroxycyclobutenones have been proven as facile diene precursors for [4+1] annulation. Meanwhile, the reported transformation presents a concise synthetic route to polysubstituted cyclopentenones with high stereoselectivity.

  已经公开了α-羟基环丁烯酮的立体控制的[4 + 1]环。首次证明了α-羟基环丁烯酮是用于[4 + 1]环化的简便二烯前体。同时，报道的转化为具有高立体选择性的多取代的环戊烯酮提供了简明的合成路线。
• A method for the stereoselective construction of 4-alkoxy-5-alkylidenecyclopentenones by the tandem ring expansion-functionalization of 1-alkynylcyclobutenols using a palladium-mercury cocatalytic system
  作者：Lanny S. Liebeskind、Agnes Bombrun

  DOI：10.1021/jo00084a038

  日期：1994.3

  1-(1-Alkynyl)-4-methoxy-4-methyl-2-cyclobutenols, prepared by nucleophilic functionalization of cyclobutenediones, were transformed with high stereoselectivity into 4-methoxy-4-methyl-5-alkylidenecyclopentenones. The action of stoichiometric Hg(OCOCF3)(2) and then metathesis with NaCl produced 5-(1-(chloromercurio)alkylidene)-4-methoxy-4-methyl-2-cyclopentenones which were stereospecifically functionalized by palladium-mediated allylation and hydroxybutenylation. Treatment with Br-2/DMSO led to stereospecific bromodemercuration. The 1-(1-alkynyl)-4-methoxy-4-methyl-2-cyclobutenols underwent efficient and very stereoselective tandem ring expansion-functionalizations in the presence of three different allylic chlorides and a catalyst system composed of 10% Hg(OCOCF3)(2) and 10% PdCl2. All products can be obtained with a stereoselectivity greater than 99:1 at the exocyclic alkene.