N-Allyl-N-tert-butyl-3-chloro-benzamide | 67616-61-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-Allyl-N-tert-butyl-3-chloro-benzamide
• CAS: 67616-61-9
• 化学式: C₁₄H₁₈ClNO
• 分子量: 251.756
• InChiKey: MERBAUDKQQZNIP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.77
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  20.31
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  甲醇 、 Langlois reagent 、 N-Allyl-N-tert-butyl-3-chloro-benzamide 在 四丁基高氯酸铵 作用下， 以 1,2-二氯乙烷 为溶剂， 以74 %的产率得到methyl tert-butyl(2-(3-chlorophenyl)-4,4,4-trifluorobutyl)carbamate
  参考文献：
  名称：

  Electrochemically‐Driven 1,4‐Aryl Migration via Radical Fluoromethylation of N‐Allylbenzamides: a Straightforward Access to Functionalized β‐Arylethylamines

  摘要：

  An electrochemical radical Truce Smiles rearrangement of N‐allylbenzamides is documented herein. The selective 1,4‐aryl migration was triggered by the radical fluoromethylation of the alkene providing a direct route to fluoro derivatives of the highly privileged β‐arylethylamine pharmacophore. This practical transformation utilizes readily available starting materials and employs an electrical current to drive the oxidative process under mild reaction conditions. It accommodates a variety of migratory aryl groups with different electronic properties and substitution patterns. Careful selection of the protecting group on the nitrogen atom of the N‐allylbenzamide is crucial to outcompete the undesired 6‐endo cyclization and achieve high level of selectivity towards the 1,4‐aryl migration. DFT calculations support the reaction mechanism and unveil the origin of selectivity between the two competitive pathways.

  DOI：

  10.1002/anie.202406017
• 作为产物：
  描述：

  3-氯苯甲酰氯 在 sodium hydride 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.75h， 生成 N-Allyl-N-tert-butyl-3-chloro-benzamide
  参考文献：
  名称：

  Electrochemically‐Driven 1,4‐Aryl Migration via Radical Fluoromethylation of N‐Allylbenzamides: a Straightforward Access to Functionalized β‐Arylethylamines

  摘要：

  An electrochemical radical Truce Smiles rearrangement of N‐allylbenzamides is documented herein. The selective 1,4‐aryl migration was triggered by the radical fluoromethylation of the alkene providing a direct route to fluoro derivatives of the highly privileged β‐arylethylamine pharmacophore. This practical transformation utilizes readily available starting materials and employs an electrical current to drive the oxidative process under mild reaction conditions. It accommodates a variety of migratory aryl groups with different electronic properties and substitution patterns. Careful selection of the protecting group on the nitrogen atom of the N‐allylbenzamide is crucial to outcompete the undesired 6‐endo cyclization and achieve high level of selectivity towards the 1,4‐aryl migration. DFT calculations support the reaction mechanism and unveil the origin of selectivity between the two competitive pathways.

  DOI：

  10.1002/anie.202406017

文献信息

• Baruffini; Vicarini; Gandini, Farmaco, Edizione Scientifica, 1978, vol. 33, # 7, p. 522 - 530
  作者：Baruffini、Vicarini、Gandini

  DOI：——

  日期：——