3-tert-Butoxy-4-methoxy-4-methyl-2-cyclobuten-1-one | 155190-46-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯酯类
• 英文名称: 3-tert-Butoxy-4-methoxy-4-methyl-2-cyclobuten-1-one
• 英文别名: 4-Methoxy-4-methyl-3-[(2-methylpropan-2-yl)oxy]cyclobut-2-en-1-one
• CAS: 155190-46-8
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: ZYFISRMGNYCTIQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-tert-Butoxy-4-methoxy-4-methyl-2-cyclobuten-1-one 在 potassium fluoride 、 lithium aluminium tetrahydride 、 正丁基锂 、 三氟乙酸 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 1-Ethynyl-4-methoxy-4-methyl-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：

  2,3-二叔丁氧基-4-羟基-2-环丁烯-1-酮 在 盐酸 作用下， 以 二氯甲烷 为溶剂， 反应 12.83h， 生成 3-tert-Butoxy-4-methoxy-4-methyl-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

• 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.