5-[2-[2-[Tert-butyl(dimethyl)silyl]ethynyl]cyclopenten-1-yl]pent-4-ynal | 210829-20-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-[2-[2-[Tert-butyl(dimethyl)silyl]ethynyl]cyclopenten-1-yl]pent-4-ynal
• CAS: 210829-20-2
• 化学式: C₁₈H₂₆OSi
• 分子量: 286.489
• InChiKey: IWNOCRUTFDASON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-[2-[2-[Tert-butyl(dimethyl)silyl]ethynyl]cyclopenten-1-yl]pent-4-ynal 、 乙基三苯基溴化膦 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 20.67h， 以90%的产率得到
  参考文献：
  名称：

  Coupling of Fischer carbene complexes with conjugated enediynes featuring radical traps: Novel structure and reactivity features of chromium complexed arene diradical species

  摘要：

  The reaction of Fischer carbene complexes with conjugated enediynes that feature a pendant alkene group has been examined. The reaction proceeds through carbene-alkyne coupling to generate an enyne-ketene intermediate. This intermediate then undergoes Moore cyclization to generate a chromium complexed arene diradical, which then undergoes cyclization with the pendant alkene group. The radical cyclization prefers the 6-endo mode unless radical-stabilizing groups are present to favor the 5-exo mode. The intermediate diradical species were evaluated computationally in both the singlet and triplet configurations. Arene triplet diradicals feature minimal spin density at oxygen and delocalization to chromium. The 6-endo cyclization product was kinetically and thermodynamically favored. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.08.003
• 作为产物：
  描述：

  5-[2-[2-[Tert-butyl(dimethyl)silyl]ethynyl]cyclopenten-1-yl]pent-4-yn-1-ol 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 Petroleum ether 为溶剂， 以96%的产率得到5-[2-[2-[Tert-butyl(dimethyl)silyl]ethynyl]cyclopenten-1-yl]pent-4-ynal
  参考文献：
  名称：

  Coupling of Fischer carbene complexes with conjugated enediynes featuring radical traps: Novel structure and reactivity features of chromium complexed arene diradical species

  摘要：

  The reaction of Fischer carbene complexes with conjugated enediynes that feature a pendant alkene group has been examined. The reaction proceeds through carbene-alkyne coupling to generate an enyne-ketene intermediate. This intermediate then undergoes Moore cyclization to generate a chromium complexed arene diradical, which then undergoes cyclization with the pendant alkene group. The radical cyclization prefers the 6-endo mode unless radical-stabilizing groups are present to favor the 5-exo mode. The intermediate diradical species were evaluated computationally in both the singlet and triplet configurations. Arene triplet diradicals feature minimal spin density at oxygen and delocalization to chromium. The 6-endo cyclization product was kinetically and thermodynamically favored. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.08.003

文献信息

• Coupling of Fischer carbene complexes with conjugated enediynes featuring radical traps: Novel structure and reactivity features of chromium complexed arene diradical species
  作者：Yi Zhang、Tareq Irshaidat、Haixia Wang、Kris V. Waynant、Haobin Wang、James W. Herndon

  DOI：10.1016/j.jorganchem.2008.08.003

  日期：2008.10

  The reaction of Fischer carbene complexes with conjugated enediynes that feature a pendant alkene group has been examined. The reaction proceeds through carbene-alkyne coupling to generate an enyne-ketene intermediate. This intermediate then undergoes Moore cyclization to generate a chromium complexed arene diradical, which then undergoes cyclization with the pendant alkene group. The radical cyclization prefers the 6-endo mode unless radical-stabilizing groups are present to favor the 5-exo mode. The intermediate diradical species were evaluated computationally in both the singlet and triplet configurations. Arene triplet diradicals feature minimal spin density at oxygen and delocalization to chromium. The 6-endo cyclization product was kinetically and thermodynamically favored. (C) 2008 Elsevier B.V. All rights reserved.