N-Phenyl-benzimidic acid (E)-hex-2-enyl ester | 206360-80-7

• 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-Phenyl-benzimidic acid (E)-hex-2-enyl ester
• CAS: 206360-80-7
• 化学式: C₁₉H₂₁NO
• 分子量: 279.382
• InChiKey: PLKDOYVWUSCEFQ-WSIXONHNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.14
• 重原子数：
  21.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  21.59
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  N-Phenyl-benzimidic acid (E)-hex-2-enyl ester 在 silver tetrafluoroborate 、 、 二甲基亚砜 作用下， 以62%的产率得到N-(1-ethenylbutyl)-N-phenylbenzamide
  参考文献：
  名称：

  First Enantioselective Catalyst for the Rearrangement of Allylic Imidates to Allylic Amides

  摘要：

  A series of Pd(II) complexes containing chiral diamine ligands were investigated as asymmetric catalysts for the rearrangement of allylic imidates to allyl amides. The best catalysts were cations obtained by dechlorination of dichloro[(S)-2-(isoindolinylmethyl)-N-methylpyrrolidine]palladium-(II) (II) (17) with silver salts in CH2Cl2. Catalyst 18 was studied thoroughly and shown by H-1 NMR and X-ray crystallography analysis to be a C-1 symmetric dimer (Figure 1). A series of related catalysts 22-27 having various counterions and anionic ligands were also prepared and studied as asymmetric catalysts for the rearrangement of allylic N-(4-trifluorophenyl)benzimidate 29 to allylic benzamide 30 (eq 4). Rearrangement of 29 in CH2Cl2 (48 h at 40 degrees C) in the presence of 5 mol % of 18 affords (-)-30 in 69% yield and 55% ee. Enantioselection is increased to 60% when an isomerically pure sample of 18 is employed. Chemical correlation of allylic benzamide 30 with (R)-norvaline established that (-)-30 has the R absolute configuration (Scheme 3). A cyclization-induced rearrangement mechanism (Scheme 1) requires that in the major pathway the imidate nitrogen attacks the re face of the olefin with Pd coordinated to the si face. These studies constitute the first report of asymmetric catalysis of the rearrangement of allylic imidates to allylic amides. However, significant hurdles remain to be overcome before the enantioselective rearrangement of allylic imidates becomes a practical route to enantioenriched nitrogen compounds.

  DOI：

  10.1021/jo962090p
• 作为产物：
  描述：

  反式-2-已烯-1-醇 、 N-苯基亚胺苄基氯 在 sodium hydride 作用下， 生成 N-Phenyl-benzimidic acid (E)-hex-2-enyl ester
  参考文献：
  名称：

  Asymmetric aza-Claisen rearrangement of allyl imidates catalyzed by homochiral cationic palladium(II) complexes

  摘要：

  The asymmetric aza-Claisen rearrangement of (E)-3-alkyl-2-propenyl N-[4-trifluoromethyl)phenyl]benzimidates was catalyzed by a homochiral cationic palladium(II) complex generated from PdCl2{(S)-2-(2-diphenylphosphino)phenyl-4-benzyloxazoline} and silver tetrafluoroborate (Pd:silver=1:1) to give (S)-N-(1-alkyl-2-propenyl)-N-[4-(trifluoromethyl)phenyl]benzamide of up to 81% ee. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00059-7

文献信息

• The first tridentate ligand for catalytic enantioselective aza-Claisen rearrangement of allylic imidates
  作者：Yutong Jiang、James M. Longmire、Xumu Zhang

  DOI：10.1016/s0040-4039(99)00007-6

  日期：1999.2

  Chiral tridentate ligand ph-ambox (1) can form a cationic Pd(II) catalyst for the [3,3]-sigmatropic rearrangement of allylic imidates to allylic amides with ees up to 83% for one substrate.

  手性三齿配体ph-ambox（1）可以形成阳离子Pd（II）催化剂，用于烯丙基酰亚胺的[3,3]-σ重排成烯丙基酰胺，对于一种底物，ee最高为83％。
• Cyclopalladated ferrocenyl amines as enantioselective catalysts for the rearrangement of allylic imidates to allylic amides
  作者：T.Keith Hollis、Larry E. Overman

  DOI：10.1016/s0040-4039(97)10385-9

  日期：1997.12

  The first examples of the use of cyclopalladated complexes in enantioselective catalysis are reported. Cyclopalladated ferrocenyl amine 6f promotes the rearrangement of some 2-alkenyl imidates to allylically transposed amides in excellent yield and moderate enantioselectivity.

  报道了在对映选择性催化中使用环palpalated配合物的第一个例子。环palladladated二茂铁基胺6f促进了一些2-烯基酰亚胺的重排为烯丙基转座的酰胺，具有出色的收率和中等的对映选择性。