((R)-1-tert-Butoxymethyl-butyl)-(4-trifluoromethyl-phenyl)-amine | 188122-63-6

• 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: ((R)-1-tert-Butoxymethyl-butyl)-(4-trifluoromethyl-phenyl)-amine
• 英文别名: N-[(2R)-1-[(2-methylpropan-2-yl)oxy]pentan-2-yl]-4-(trifluoromethyl)aniline
• CAS: 188122-63-6
• 化学式: C₁₆H₂₄F₃NO
• 分子量: 303.368
• InChiKey: YIBSOEZYMGQVHR-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ((R)-1-tert-Butoxymethyl-butyl)-(4-trifluoromethyl-phenyl)-amine 在 氢溴酸 、 溶剂黄146 作用下， 反应 0.67h， 以47%的产率得到(R)-2-(4-Trifluoromethyl-phenylamino)-pentan-1-ol
  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：

  (R)-(-)-2-氨基-1-戊醇 在 tris(dibenzylideneacetone)dipalladium (0) 、 硫酸 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 sodium t-butanolate 作用下， 以 二氯甲烷 为溶剂， 生成 ((R)-1-tert-Butoxymethyl-butyl)-(4-trifluoromethyl-phenyl)-amine
  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

文献信息

• First Enantioselective Catalyst for the Rearrangement of Allylic Imidates to Allylic Amides
  作者：Michael Calter、T. Keith Hollis、Larry E. Overman、Joseph Ziller、G. Greg Zipp

  DOI：10.1021/jo962090p

  日期：1997.3.1

  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.