3-Chloro-5,5-bis-hydroxymethyl-3-vinyl-cyclohexanol | 656835-13-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-Chloro-5,5-bis-hydroxymethyl-3-vinyl-cyclohexanol
• 英文别名: 3-Chloro-3-ethenyl-5,5-bis(hydroxymethyl)cyclohexan-1-ol；3-chloro-3-ethenyl-5,5-bis(hydroxymethyl)cyclohexan-1-ol
• CAS: 656835-13-1
• 化学式: C₁₀H₁₇ClO₃
• 分子量: 220.696
• InChiKey: UNZLLXAUWYVPCL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  60.7
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 3-Chloro-5,5-bis-hydroxymethyl-3-vinyl-cyclohexanol 在 吡啶 作用下， 以85%的产率得到Acetic acid (1S,3R,5R)-3-acetoxy-5-vinyl-6-oxa-bicyclo[3.2.1]oct-1-ylmethyl 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
• 作为产物：
  描述：

  dimethyl 2-(2-((tert-butyldiphenylsilyl)oxy)ethyl)malonate 在 bis-triphenylphosphine-palladium(II) chloride 、 bis(1,5-cyclooctadiene)nickel (0) 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 二异丁基氢化铝 、 三苯基膦 、 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， 反应 1.08h， 生成 3-Chloro-5,5-bis-hydroxymethyl-3-vinyl-cyclohexanol
  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.