tert-butyl 2,4-dichlorobenzylidenecarbamate | 163226-26-4

• 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: tert-butyl 2,4-dichlorobenzylidenecarbamate
• 英文别名: tert-butyl N-[(2,4-dichlorophenyl)methylidene]carbamate
• CAS: 163226-26-4
• 化学式: C₁₂H₁₃Cl₂NO₂
• 分子量: 274.147
• InChiKey: FCYVQUDMDMMIEE-UHFFFAOYSA-N

物化性质

• 沸点：
  342.5±52.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl 2,4-dichlorobenzylidenecarbamate 在 sodium tetrahydroborate 、 (1R,2R)-N¹,N²-bis[4-(1-pyrrolidinyl)-2-quinolinyl]-1,2-cyclohexanediamine 、 ammonium acetate 、 cobalt(II) chloride 作用下， 以 甲醇 、 水 、 甲苯 为溶剂， 反应 68.0h， 生成 (R)-tert-butyl (1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethyl)carbamate
  参考文献：
  名称：

  Organocatalytic, Enantioselective Synthesis of VNI: A Robust Therapeutic Development Platform for Chagas, a Neglected Tropical Disease

  摘要：

  VNI is a potent inhibitor of CYP51 and was recently shown to achieve a parasitological cure of mice infected with T. cruzi in both acute and chronic stages of infection. T. cruzi is the causative parasite of Chagas disease, a neglected tropical disease. The first enantioselective chemical synthesis of VNI (at a materials cost of less than $0.10/mg) is described. Furthermore, the key enantioselective step is performed at the 10 g scale.

  DOI：

  10.1021/ol303092v
• 作为产物：
  描述：

  tetr-butyl ((2,4-dichlorophenyl)(phenylsulfonyl)methyl)carbamate 在 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 tert-butyl 2,4-dichlorobenzylidenecarbamate
  参考文献：
  名称：

  直接催化不对称曼尼希型反应生成α-羟基-β-氨基酸衍生物

  摘要：

  实现了α-氧官能化酰胺的直接催化曼尼希型反应。在含有软路易斯酸和布朗斯台德碱的协同催化体系中，使用7-氮杂吲哚啉酰胺对于促进直接烯胺化和随后向亚胺的立体选择性加成至关重要。该操作简单的室温方案提供了具有高立体选择性的顺曼尼希加合物。产物酰胺部分的不同官能团转化使得可以迅速获得对映体富集的顺式α-羟基-β-氨基羧酸衍生物，从而突出了本发明催化剂的合成用途。

  DOI：

  10.1021/acs.orglett.7b03609

文献信息

• α-Halo Amides as Competent Latent Enolates: Direct Catalytic Asymmetric Mannich-Type Reaction
  作者：Bo Sun、Pandur Venkatesan Balaji、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1021/jacs.7b03291

  日期：2017.6.21

  dehalogenation and thus largely neglected as enolate precursors in catalytic enantioselective C-C bond-forming reactions. By merging the increased stability of the α-C-halogen bond of amides and the direct enolization methodology of the designed amide, we explored a direct catalytic asymmetric Mannich-type reaction of α-halo 7-azaindoline amides with N-carbamoyl imines. All α-halo substituents, α-F, -Cl, -Br, -I

  α-卤代羰基化合物易于脱卤，因此在催化对映选择性 CC 键形成反应中作为烯醇前体在很大程度上被忽视。通过将酰胺的 α-C-卤素键的稳定性提高和设计酰胺的直接烯醇化方法相结合，我们探索了 α-卤代 7-氮杂二氢吲哚酰胺与 N-氨基甲酰基亚胺的直接催化不对称曼尼希型反应。所有 α-卤素取代基，α-F、-Cl、-Br、-I 酰胺都可以耐受，以高度立体选择性的方式提供曼尼希加合物，而不会发生不希望的脱卤。非对映选择性根据芳族亚胺的取代模式发生有趣的变化，这归因于基于开放过渡态模型的立体化学分化。
• Electrophilic amination reagents: A new method for the preparation of 3-Aryl-N-BOC (or N-FMOC) oxaziridines
  作者：Joe¨lle Vidal、Ste´phanie Damestoy、Andre´ Collet

  DOI：10.1016/0040-4039(95)00025-8

  日期：1995.2

  N-BOC or N-FMOC benzaldimines are oxidized to the corresponding 3-Aryl-N-BOC or N-FMOC oxaziridines by reaction with Li m-chloroperoxybenzoate under aprotic conditions. The new oxaziridines can transfer their N-BOC or N-FMOC group to morpholine to give the corresponding Nβ-protected hydrazines.

  通过在非质子条件下与间氯过氧苯甲酸锂反应，将N-BOC或N-FMOC苯甲二胺氧化为相应的3-芳基-N-BOC或N-FMOC恶唑烷。新的氧氮环丙烷可以在其N-BOC或N-FMOC基团转移到吗啉，得到相应的N β -保护的肼。
• N-Alkyloxycarbonyl-3-aryloxaziridines: Their Preparation, Structure, and Utilization As Electrophilic Amination Reagents
  作者：Joëlle Vidal、Stéphanie Damestoy、Laure Guy、Jean-Christophe Hannachi、André Aubry、Andreé Collet、André Aubry

  DOI：10.1002/chem.19970031019

  日期：1997.10

  AbstractThis paper reports the synthesis of a series of N‐protected oxaziridines (N‐Moc, Boc, Z or Fmoc) and discusses their ability to deliver their N‐alkoxycar‐bonyl fragment to amines, enolates, sulfur, and phosphorus nucleophiles (electrophilic amination). These oxaziridines are prepared by oxidation of the corresponding imines with oxone or anhydrous MCPBA lithium salt as the source of oxygen. They transfer their N‐protected fragment to primary and secondary amines to give protected hydrazines in fair to excellent yield. The nitrogen transfer to free amino acids (in form of their R4N+ salts) is particularly fast, even at low temperature, providing L (or D) N‐protected α‐hydrazino acids. Enolates are C‐aminated to give N‐protected α‐amino ketones, esters, or amides in modest yield, due to a side aldol reaction of the unreacted enolate with the released benzaldehyde. With tertiary amines (Et3N), sulfides (PhSMe), and phosphines (Ph3P), amination and oxidation proceed in a parallel way; the amount of amination product increases when the temperature is lowered (kinetic control). Some of the factors that can orient the oxaziridine reactivity towards amination or oxidation of nucleophiles are considered.