1,3-Dioxane-5-acetaldehyde,2,2-dimethyl-5-[2-methylene-4-(trimethylsilyl)-3-butenyl]- | 656835-29-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,3-Dioxane-5-acetaldehyde,2,2-dimethyl-5-[2-methylene-4-(trimethylsilyl)-3-butenyl]-
• 英文别名: [2,2-Dimethyl-5-((E)-2-methylene-4-trimethylsilanyl-but-3-enyl)-[1,3]dioxan-5-yl]-acetaldehyde
• CAS: 656835-29-9
• 化学式: C₁₆H₂₈O₃Si
• 分子量: 296.482
• InChiKey: MBIBIEBFJRRVDU-UHFFFAOYSA-N

物化性质

• 沸点：
  354.4±17.0 °C(Predicted)
• 密度：
  0.923±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.72
• 重原子数：
  20.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1,3-Dioxane-5-acetaldehyde,2,2-dimethyl-5-[2-methylene-4-(trimethylsilyl)-3-butenyl]- 在 bis(1,5-cyclooctadiene)nickel (0) 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以39%的产率得到3,3-Dimethyl-10-((E)-2-trimethylsilanyl-vinyl)-2,4-dioxa-spiro[5.5]undec-9-en-8-one
  参考文献：
  名称：

  Further studies on Ni(0)-catalyzed cyclization of a branched 1,3-diene and tethered aldehyde via oxa-nickelacycle intermediate

  摘要：

  The reactivity of oxa-nickelacycles 7, generated by the reaction of a branched 1,3-diene and tethered carbonyl group with a Ni(0) complex, was investigated in detail. It was found that oxa-nickelacycles 7 are relatively stable and that P-hydride elimination from 7 occurred at a high temperature, producing the cyclized dienes 51 and/or 52 in good yields. This Ni(0)-catalyzed cyclization via beta-hydride elimination from oxa-nickelacycles tolerated various substituents on the diene moiety and could be applied to a five- to seven-membered ring construction. Next, transmetalation of oxa-nickelacycle 7 with various organometallic reagents was investigated. It was found that the tandem reaction, i.e. cyclization of 6 followed by transmetalation of the resulting oxa-nickelacycle 7, proceeded smoothly, giving 53 and/or 54 in good yields. In addition, the catalytic cycle in this transmetalation reaction was also established. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2003.08.027
• 作为产物：
  描述：

  2-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2-(2-iodo-allyl)-malonic acid dimethyl ester 在 bis-triphenylphosphine-palladium(II) chloride 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 生成 1,3-Dioxane-5-acetaldehyde,2,2-dimethyl-5-[2-methylene-4-(trimethylsilyl)-3-butenyl]-
  参考文献：
  名称：

  Further studies on Ni(0)-catalyzed cyclization of a branched 1,3-diene and tethered aldehyde via oxa-nickelacycle intermediate

  摘要：

  The reactivity of oxa-nickelacycles 7, generated by the reaction of a branched 1,3-diene and tethered carbonyl group with a Ni(0) complex, was investigated in detail. It was found that oxa-nickelacycles 7 are relatively stable and that P-hydride elimination from 7 occurred at a high temperature, producing the cyclized dienes 51 and/or 52 in good yields. This Ni(0)-catalyzed cyclization via beta-hydride elimination from oxa-nickelacycles tolerated various substituents on the diene moiety and could be applied to a five- to seven-membered ring construction. Next, transmetalation of oxa-nickelacycle 7 with various organometallic reagents was investigated. It was found that the tandem reaction, i.e. cyclization of 6 followed by transmetalation of the resulting oxa-nickelacycle 7, proceeded smoothly, giving 53 and/or 54 in good yields. In addition, the catalytic cycle in this transmetalation reaction was also established. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2003.08.027