3-cyclohexyl-3,3-dideutropropyne | 1532556-12-9

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: 3-cyclohexyl-3,3-dideutropropyne
• CAS: 1532556-12-9
• 化学式: C₉H₁₄
• 分子量: 124.194
• InChiKey: UARFKZSJGDQRLF-NCYHJHSESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.59
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  3-cyclohexyl-3,3-dideutropropyne 、 苯甲酸 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 双(2-二苯基磷苯基)醚 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 8.0h， 生成 、
  参考文献：
  名称：

  Mechanistic Investigations of the Rhodium Catalyzed Propargylic CH Activation

  摘要：

  Previously we reported the redox-neutral atom economic rhodium catalyzed coupling of terminal alkynes with carboxylic acids using the DPEphos ligand. We herein present a thorough mechanistic investigation applying various spectroscopic and spectrometric methods (NMR, in situ-IR, ESI-MS) in combination with DFT calculations. Our findings show that in contrast to the originally proposed mechanism, the catalytic cycle involves an intramolecular protonation and not an oxidative insertion of rhodium in the OH bond of the carboxylic acid. A sigma-allyl complex was identified as the resting state of the catalytic transformation and characterized by X-ray crystallographic analysis. By means of ESI-MS investigations we were able to detect a reactive intermediate of the catalytic cycle.

  DOI：

  10.1021/ja411204d
• 作为产物：
  描述：

  环己基乙醛 在 吡啶 、 正丁基锂 、 重水 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 38.0h， 生成 3-cyclohexyl-3,3-dideutropropyne
  参考文献：
  名称：

  Mechanistic Investigations of the Rhodium Catalyzed Propargylic CH Activation

  摘要：

  Previously we reported the redox-neutral atom economic rhodium catalyzed coupling of terminal alkynes with carboxylic acids using the DPEphos ligand. We herein present a thorough mechanistic investigation applying various spectroscopic and spectrometric methods (NMR, in situ-IR, ESI-MS) in combination with DFT calculations. Our findings show that in contrast to the originally proposed mechanism, the catalytic cycle involves an intramolecular protonation and not an oxidative insertion of rhodium in the OH bond of the carboxylic acid. A sigma-allyl complex was identified as the resting state of the catalytic transformation and characterized by X-ray crystallographic analysis. By means of ESI-MS investigations we were able to detect a reactive intermediate of the catalytic cycle.

  DOI：

  10.1021/ja411204d