(+/-)-1-{3-[(1,1-dimethylethyl)dimethylsilyloxy]-2-methylcyclohex-2-enyl}-4-methylpent-3-en-2-one | 925896-54-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (+/-)-1-{3-[(1,1-dimethylethyl)dimethylsilyloxy]-2-methylcyclohex-2-enyl}-4-methylpent-3-en-2-one
• 英文别名: 1-[3-[Tert-butyl(dimethyl)silyl]oxy-2-methylcyclohex-2-en-1-yl]-4-methylpent-3-en-2-one；1-[3-[tert-butyl(dimethyl)silyl]oxy-2-methylcyclohex-2-en-1-yl]-4-methylpent-3-en-2-one
• CAS: 925896-54-4
• 化学式: C₁₉H₃₄O₂Si
• 分子量: 322.563
• InChiKey: OKKSCJDNECEUQZ-UHFFFAOYSA-N

物化性质

• 沸点：
  377.3±25.0 °C(Predicted)
• 密度：
  0.92±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.01
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-1-{3-[(1,1-dimethylethyl)dimethylsilyloxy]-2-methylcyclohex-2-enyl}-4-methylpent-3-en-2-one 在 三甲基铝 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 120.0h， 以89%的产率得到(+/-)-(4aRS,8aRS)-6-[(1,1-dimethylethyl)dimethylsilyl]oxy-8,8,8a-trimethyl-3,4,4a,5,8,8a-hexahydronaphthalen-1(2H)-one
  参考文献：
  名称：

  Stepwise Acid-Promoted Double-Michael Process:  An Alternative to Diels−Alder Cycloadditions for Hindered Silyloxydiene−Dienophile Pairs

  摘要：

  The hindered diene 1 reacts with 3-methylcyclohexenone 6 catalyzed by triflimide to produce the Mukaiyama Michael product 7 (low-temperature quenching) or the [4+2] cycloadduct 8 (quenching at 0 degrees C). Reaction of the hindered diene 23 with 2-methylcyclohexenone 12 with 5:1 AlBr3:AlMe3 afforded a 71% yield of a 1.9:1 mixture of two cycloadducts. Hydrolysis of the major isomer gave the dione 27', a model for the BCD ring system of pentacyclic triterpenes.

  DOI：

  10.1021/ol062980j
• 作为产物：
  描述：

  4-甲基-3戊烯-2-酮 在 双三氟甲烷磺酰亚胺 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.33h， 生成 (+/-)-1-{3-[(1,1-dimethylethyl)dimethylsilyloxy]-2-methylcyclohex-2-enyl}-4-methylpent-3-en-2-one
  参考文献：
  名称：

  Stepwise Acid-Promoted Double-Michael Process:  An Alternative to Diels−Alder Cycloadditions for Hindered Silyloxydiene−Dienophile Pairs

  摘要：

  The hindered diene 1 reacts with 3-methylcyclohexenone 6 catalyzed by triflimide to produce the Mukaiyama Michael product 7 (low-temperature quenching) or the [4+2] cycloadduct 8 (quenching at 0 degrees C). Reaction of the hindered diene 23 with 2-methylcyclohexenone 12 with 5:1 AlBr3:AlMe3 afforded a 71% yield of a 1.9:1 mixture of two cycloadducts. Hydrolysis of the major isomer gave the dione 27', a model for the BCD ring system of pentacyclic triterpenes.

  DOI：

  10.1021/ol062980j

文献信息

• Stepwise Acid-Promoted Double-Michael Process:  An Alternative to Diels−Alder Cycloadditions for Hindered Silyloxydiene−Dienophile Pairs
  作者：Michael E. Jung、David G. Ho

  DOI：10.1021/ol062980j

  日期：2007.1.1

  The hindered diene 1 reacts with 3-methylcyclohexenone 6 catalyzed by triflimide to produce the Mukaiyama Michael product 7 (low-temperature quenching) or the [4+2] cycloadduct 8 (quenching at 0 degrees C). Reaction of the hindered diene 23 with 2-methylcyclohexenone 12 with 5:1 AlBr3:AlMe3 afforded a 71% yield of a 1.9:1 mixture of two cycloadducts. Hydrolysis of the major isomer gave the dione 27', a model for the BCD ring system of pentacyclic triterpenes.