2-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2-(2-iodo-allyl)-malonic acid dimethyl ester | 656834-99-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2-(2-iodo-allyl)-malonic acid dimethyl ester
• CAS: 656834-99-0
• 化学式: C₂₆H₃₃IO₅Si
• 分子量: 580.535
• InChiKey: ZPEVVMXXWASREN-UHFFFAOYSA-N

物化性质

• 沸点：
  543.7±50.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.62
• 重原子数：
  33.0
• 可旋转键数：
  10.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2-(2-iodo-allyl)-malonic acid dimethyl ester 在 bis-triphenylphosphine-palladium(II) chloride 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 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 2-[2,2-Dimethyl-5-(2-methylidenebut-3-en-1-yl)-1,3-dioxan-5-yl]ethan-1-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：

  2-iodo-2-propenyl methanesulfonate 、 dimethyl 2-(2-((tert-butyldiphenylsilyl)oxy)ethyl)malonate 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以71%的产率得到2-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-2-(2-iodo-allyl)-malonic acid dimethyl ester
  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