1-氨基金刚烷-2,2,2′,2′,2″,2″-d6 | 1219805-53-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 1-氨基金刚烷-2,2,2′,2′,2″,2″-d6
• 中文别名: 金刚烷胺-D6氘代；1-氨基金刚烷-D6(金刚烷胺-D6)；4-溴-2-(1-哌嗪)苯甲酸；金刚烷胺-D6氘代内标
• 英文名称: Amantadine-d6
• 英文别名: 2,2,8,8,9,9-hexadeuterioadamantan-1-amine
• CAS: 1219805-53-4
• 化学式: C₁₀H₁₇N
• 分子量: 157.204
• InChiKey: DKNWSYNQZKUICI-KETLRHEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-氨基金刚烷-2,2,2′,2′,2″,2″-d6 在 lithium aluminium tetrahydride 、 potassium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 130.0 ℃ 、800.01 kPa 条件下， 反应 3.67h， 生成
  参考文献：
  名称：

  Carboxylate-Assisted C(sp³)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes

  摘要：

  The mechanism of C H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation-deprotonation mechanism with Delta G(298K)double dagger = 22.2 +/- 0.1 kcal.mol(-1) for the parent N-adamantyl-N'-mesityl complex. An experimentally determined Delta S double dagger = 5.2 +/- 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp(3))-H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 +/- 1.7), agree closely with a computed six-membered carboxylate-assisted C H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment.

  DOI：

  10.1021/ja5021958

文献信息

• Carboxylate-Assisted C(sp³)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes
  作者：Jeffrey S. Cannon、Lufeng Zou、Peng Liu、Yu Lan、Daniel J. O’Leary、K. N. Houk、Robert H. Grubbs

  DOI：10.1021/ja5021958

  日期：2014.5.7

  The mechanism of C H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation-deprotonation mechanism with Delta G(298K)double dagger = 22.2 +/- 0.1 kcal.mol(-1) for the parent N-adamantyl-N'-mesityl complex. An experimentally determined Delta S double dagger = 5.2 +/- 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp(3))-H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 +/- 1.7), agree closely with a computed six-membered carboxylate-assisted C H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment.