1,3-Dioxane-5-acetaldehyde, 2,2-dimethyl-5-(2-methylene-3-butenyl)- | 212051-02-0

• 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-3-butenyl)-
• 英文别名: 2-[2,2-dimethyl-5-(2-methylidenebut-3-enyl)-1,3-dioxan-5-yl]acetaldehyde
• CAS: 212051-02-0
• 化学式: C₁₃H₂₀O₃
• 分子量: 224.3
• InChiKey: RYWSVIVTHSBSHO-UHFFFAOYSA-N

物化性质

• 沸点：
  301.8±17.0 °C(Predicted)
• 密度：
  0.944±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  1,3-Dioxane-5-acetaldehyde, 2,2-dimethyl-5-(2-methylene-3-butenyl)- 在 bis(1,5-cyclooctadiene)nickel (0) 三苯基膦 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 生成 3,3,8-Trimethyl-10-vinyl-2,4-dioxa-spiro[5.5]undec-9-en-8-ol
  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：

  dimethyl 2-(2-((tert-butyldiphenylsilyl)oxy)ethyl)malonate 在 bis-triphenylphosphine-palladium(II) chloride 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 二异丁基氢化铝 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 1,3-Dioxane-5-acetaldehyde, 2,2-dimethyl-5-(2-methylene-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

文献信息

• Nickel (0)-catalyzed diene-aldehyde cyclization
  作者：Yoshihiro Sato、Tetsuya Takanashi、Megumi Hoshiba、Miwako Mori

  DOI：10.1016/s0040-4039(98)01125-3

  日期：1998.7

  Nickel (0)-catalyzed diene-aldehyde cyclization was realized. In this reaction, oxidative cyclization between diene and aldehyde moiety occurs to give π-allylnickel complex, and then β-hydride elimination occurs to give cyclized diene. Various diene-aldehydes having substituents on the diene gave the cyclized products using Ni (0) in good to moderate yields.

  实现了镍（0）催化的二烯-醛环化。在该反应中，二烯和醛部分之间发生氧化环化，得到π-烯丙基镍配合物，然后发生β-氢化物消除，得到环化的二烯。在二烯上具有取代基的各种二烯-醛使用Ni（0）以良好至中等的产率得到环化产物。