(+/-)-2-azido-2-cyclohexylethanol | 1016973-35-5

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: (+/-)-2-azido-2-cyclohexylethanol
• 英文别名: 2-Azido-2-cyclohexylethan-1-ol；2-azido-2-cyclohexylethanol
• CAS: 1016973-35-5
• 化学式: C₈H₁₅N₃O
• 分子量: 169.227
• InChiKey: KNYCXGYZSQKSNM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  34.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-2-azido-2-cyclohexylethanol 、 4-叔丁基环己酮 在 三氟化硼乙醚 、 氢氧化钾 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以0.35 g的产率得到5-tert-butyl-1-(1-cyclohexyl-2-hydroxyethyl)azepan-2-one
  参考文献：
  名称：

  叠氮化物介导的不对称环膨胀反应中的非键，有吸引力的阳离子-π相互作用

  摘要：

  The influence of attractive, nonbonded interactions on the reactions of 1,2- and 1,3-hydroxyalkyl azides with ketones has been investigated through experimental and computational means. A series of 1,3-hydroxyalkyl azides bearing electronically tuned aromatic groups at the 2 position were prepared and reacted along with several derivatives designed to conformationally restrict the rotational orientation of the aromatic substituent. These studies showed that a cation-pi interaction between an aryl moiety and an N-2(+) leaving group plays a role in determining the stereoselectivity of these reactions. A series of ab initio calculations supported this hypothesis. A computational and experimental analysis suggested a primarily steric model for the analogous reactions of substituted 2-azido-1-ethanol analogues.

  DOI：

  10.1021/jo800222r
• 作为产物：
  描述：

  (+/-)-(2-azido-2-cyclohexylethoxy)triisopropylsilane 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以96%的产率得到(+/-)-2-azido-2-cyclohexylethanol
  参考文献：
  名称：

  叠氮化物介导的不对称环膨胀反应中的非键，有吸引力的阳离子-π相互作用

  摘要：

  The influence of attractive, nonbonded interactions on the reactions of 1,2- and 1,3-hydroxyalkyl azides with ketones has been investigated through experimental and computational means. A series of 1,3-hydroxyalkyl azides bearing electronically tuned aromatic groups at the 2 position were prepared and reacted along with several derivatives designed to conformationally restrict the rotational orientation of the aromatic substituent. These studies showed that a cation-pi interaction between an aryl moiety and an N-2(+) leaving group plays a role in determining the stereoselectivity of these reactions. A series of ab initio calculations supported this hypothesis. A computational and experimental analysis suggested a primarily steric model for the analogous reactions of substituted 2-azido-1-ethanol analogues.

  DOI：

  10.1021/jo800222r

文献信息

• Highly Stereoselective Ring Expansion Reactions Mediated by Attractive Cation-n Interactions
  作者：Timothy Ribelin、Christopher E. Katz、Donna G. English、Sherriel Smith、Anna K. Manukyan、Victor W. Day、Benjamin Neuenswander、Jennifer L. Poutsma、Jeffrey Aubé

  DOI：10.1002/anie.200801591

  日期：2008.8.4

  Electrostatic control of leaving group stereochemistry leads to superior diastereoselectivity in an asymmetric ring expansion reaction.