3,3-二甲基-10-戊-4-烯亚基-2,4-二氧杂螺[5.5]十一烷-8-醇 | 656835-33-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 3,3-二甲基-10-戊-4-烯亚基-2,4-二氧杂螺[5.5]十一烷-8-醇
• 英文名称: 3,3-Dimethyl-10-(pent-4-en-1-ylidene)-2,4-dioxaspiro[5.5]undecan-8-ol
• 英文别名: 3,3-dimethyl-10-pent-4-enylidene-2,4-dioxaspiro[5.5]undecan-8-ol
• CAS: 656835-33-5
• 化学式: C₁₆H₂₆O₃
• 分子量: 266.381
• InChiKey: QGIMETKMZSITGK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-[2,2-Dimethyl-5-(2-methylidenebut-3-en-1-yl)-1,3-dioxan-5-yl]ethan-1-ol 在 bis(1,5-cyclooctadiene)nickel (0) 三苯基膦 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.08h， 生成 3,3-二甲基-10-戊-4-烯亚基-2,4-二氧杂螺[5.5]十一烷-8-醇
  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

• Further studies on Ni(0)-catalyzed cyclization of a branched 1,3-diene and tethered aldehyde via oxa-nickelacycle intermediate
  作者：Yoshihiro Sato、Tetsuya Takanashi、Megumi Hoshiba、Miwako Mori

  DOI：10.1016/j.jorganchem.2003.08.027

  日期：2003.12

  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.