(E)-N-(2-ethyl-1-phenylpent-2-enyl)-P,P-diphenylphosphinamide

• 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: (E)-N-(2-ethyl-1-phenylpent-2-enyl)-P,P-diphenylphosphinamide
• 英文别名: N-(2-ethyl-1-phenylpent-2-enyl)-P,P-diphenylphosphinamide；(E)-N-diphenylphosphoryl-2-ethyl-1-phenylpent-2-en-1-amine
• 化学式: C₂₅H₂₈NOP
• 分子量: 389.477
• InChiKey: OBTSOKACXXMJOC-KGENOOAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-己炔 、 N-亚苄基-P,P-二苯基次膦酸酰胺 在 Schwartz's reagent 、 Dimethylzinc 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 4.16h， 以72%的产率得到(E)-N-(2-ethyl-1-phenylpent-2-enyl)-P,P-diphenylphosphinamide
  参考文献：
  名称：

  Dimethylzinc-Mediated Additions of Alkenylzirconocenes to Aldimines. New Methodologies for Allylic Amine and C-Cyclopropylalkylamine Syntheses

  摘要：

  Hydrozirconation of alkynes with zirconocene hydrochloride followed by in situ transmetalation to dimethylzinc provides access to reactive alkenyl organometallic reagents from readily available precursors. Upon addition of imines, 1,2-attack leads to synthetically useful allylic amine building blocks. In the presence of CH2I2 or CH2Cl2, the N-metalated allylic amide intermediate is cyclopropanated and C-cyclopropylalkylamines are formed in high yield and excellent diastereoselectivities favoring the anti products. The use of enynes as starting materials for this domino reaction provides conjugated biscyclopropanes and thus allows the stereoselective formation of five new carbon-carbon bonds. A transition state that explains the need for both zirconocene complex and alkyl zinc in the cyclopropanation reaction is proposed.

  DOI：

  10.1021/ja028092a

文献信息

• Microwave-assisted synthesis of allylic amines: considerable rate acceleration in the hydrozirconation–transmetalation–aldimine addition sequence
  作者：Peter Wipf、Jelena Janjic、Corey R. J. Stephenson

  DOI：10.1039/b316741k

  日期：——

  dimethylzinc-mediated addition of alkenylzirconocenes to diphenylphosphinoyl imines can be greatly accelerated with microwave irradiation, resulting in a convenient and rapid one-pot process for the preparation of synthetically useful allylic amines.

  微波辐射可以大大加速炔烃与盐酸锆茂的加氢锆化反应以及二甲基锌介导的烯基锆茂向二苯基膦酰基亚胺的加成反应，从而为制备合成有用的烯丙基胺提供了方便，快速的一锅法。
• Dimethylzinc-Mediated Additions of Alkenylzirconocenes to Aldimines. New Methodologies for Allylic Amine and <i>C</i>-Cyclopropylalkylamine Syntheses
  作者：Peter Wipf、Christopher Kendall、Corey R. J. Stephenson

  DOI：10.1021/ja028092a

  日期：2003.1.1

  Hydrozirconation of alkynes with zirconocene hydrochloride followed by in situ transmetalation to dimethylzinc provides access to reactive alkenyl organometallic reagents from readily available precursors. Upon addition of imines, 1,2-attack leads to synthetically useful allylic amine building blocks. In the presence of CH2I2 or CH2Cl2, the N-metalated allylic amide intermediate is cyclopropanated and C-cyclopropylalkylamines are formed in high yield and excellent diastereoselectivities favoring the anti products. The use of enynes as starting materials for this domino reaction provides conjugated biscyclopropanes and thus allows the stereoselective formation of five new carbon-carbon bonds. A transition state that explains the need for both zirconocene complex and alkyl zinc in the cyclopropanation reaction is proposed.