N-(4-Trifluoromethyl-phenyl)-N-((R)-1-vinyl-butyl)-benzamide | 188122-53-4

• 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-(4-Trifluoromethyl-phenyl)-N-((R)-1-vinyl-butyl)-benzamide
• 英文别名: N-[(3R)-hex-1-en-3-yl]-N-[4-(trifluoromethyl)phenyl]benzamide
• CAS: 188122-53-4
• 化学式: C₂₀H₂₀F₃NO
• 分子量: 347.38
• InChiKey: MLQXSIGTLFCQED-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(4-Trifluoromethyl-phenyl)-N-((R)-1-vinyl-butyl)-benzamide 在 sodium tetrahydroborate 、 臭氧 作用下， 生成 (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：

  N-(4-Trifluoromethyl-phenyl)-benzimidic acid (E)-hex-2-enyl ester 在 chiral ferrocenyloxazoline palladacycle catalyst 、 silver trifluoroacetate 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 生成 N-(4-Trifluoromethyl-phenyl)-N-((S)-1-vinyl-butyl)-benzamide 、 N-(4-Trifluoromethyl-phenyl)-N-((R)-1-vinyl-butyl)-benzamide
  参考文献：
  名称：

  手性烯丙基胺的催化不对称合成。二茂铁恶唑啉Palladacycle催化剂和酰亚胺基团的评估

  摘要：

  合成了基于二茂铁二恶唑啉五环（FOP）支架的钯（II）催化剂，并评估了前手性烯丙基N-（4-甲氧基苯基）苯甲酰胺酸酯的重排。当碘化物桥接的二聚体FOP预催化剂通过与过量的三氟乙酸银反应而活化时，E和Z前手性伯烯丙基N-（4-甲氧基苯基）苯并咪唑酯的烯丙基重排在室温发生，从而得到相应的手性烯丙基N-（4-甲氧基苯基）苯甲酰胺，高收率和良好的ee（通常为81-95％）。还评估了几种亚胺基亚氨酸酯基序。因为相应的对映体富集的烯丙基酰胺产物可以以高收率脱保护以得到对映体富集的烯丙基胺，所以烯丙基N-芳基三氟乙酰亚氨酸酯被鉴定为有前途的底物。

  DOI：

  10.1021/jo048490r

文献信息

• Palladium complexes of bis(acyclic diaminocarbene) ligands with chiral N-substituents and 8-membered chelate rings
  作者：Yoshitha A. Wanniarachchi、Sri S. Subramanium、LeGrande M. Slaughter

  DOI：10.1016/j.jorganchem.2009.06.007

  日期：2009.9

  with N,N′-bis[(R)-1-(1-naphthyl)ethyl]-1,3-diaminopropane did not lead to an isolable bis(carbene) complex, instead forming significant amounts of bis(ammonium) salt as a decomposition product. However, reaction of the same palladium isocyanide precursor with a mixture of all diastereomers of N,N′-bis[1-(1-naphthyl)ethyl]-1,3-diaminopropane provided an achiral, Cs-symmetric palladium bis(acyclic diaminocarbene)

  的反应顺-dichloridobis（p -trifluoromethylphenylisocyanide）钯（II）与Ñ，Ñ ' -双[（[R）-1-苯乙基] -1,3-二氨基丙烷，得到对映体纯，c ^ 1 -对称双（无环diaminocarbene） PdCl 2络合物的产率为41％。该配合物的X射线晶体结构表明，四个卡宾氮中的三个被扭出了与卡宾单元的共轭，这显然是由于一个苯基与螯合物的丙烯主链之间的空间相互作用所致。用类似的反应Ñ，Ñ ' -双[（ř）-1-（1-萘基乙基）-1,3-二氨基丙烷不会生成可分离的双（卡宾）络合物，而是形成大量的双（铵）盐作为分解产物。然而，相同的钯异氰化物前体与N，N'-双[1-（1-（萘基）乙基] -1,3-二氨基丙烷的所有非对映异构体的混合物的反应提供了一个非手性，C s-对称的钯双（无环）二氨基卡宾）络合物仅由（R，S）二胺衍生而来，产率为20％。
• 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。
• Planar-chiral cyclopalladated ferrocenyl amines and imines as enantioselective catalysts for allylic imidate rearrangements
  作者：Frederick Cohen、Larry E. Overman

  DOI：10.1016/s0957-4166(98)00341-3

  日期：1998.9

  A series of enantiopure cyclopalladated ferrocenyl amines and imines were synthesized and evaluated as catalysts for the [3,3]-rearrangement of allylic benzimidates to allylic benzamides. Yields and extent of enantioselection were found to be highly dependent upon the counter-ion, with a high of 78% yield and 73% ee being realized under optimum conditions.

  合成了一系列对映体纯的环palpalated的二茂铁基胺和亚胺，并将其评估为烯丙基苯甲酸酯[3,3]重排为烯丙基苯甲酰胺的催化剂。发现对映体的收率和程度高度依赖于抗衡离子，在最佳条件下可实现78％的高收率和73％ee的高收率。
• Asymmetric aza-Claisen rearrangement of allyl imidates catalyzed by homochiral cationic palladium(II) complexes
  作者：Yasuhiro Uozumi、Kazuhiko Kato、Tamio Hayashi

  DOI：10.1016/s0957-4166(98)00059-7

  日期：1998.3

  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.