N,N-diisopropyl-2-(1-trimethylsilyl)ethylbenzamide | 159888-30-9

• 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,N-diisopropyl-2-(1-trimethylsilyl)ethylbenzamide
• 英文别名: (S)-N,N-diisopropyl-2-(1-trimethylsilylethyl)benzamide；N,N-di(propan-2-yl)-2-[(1S)-1-trimethylsilylethyl]benzamide
• CAS: 159888-30-9
• 化学式: C₁₈H₃₁NOSi
• 分子量: 305.536
• InChiKey: GCDXYEHPCWSIDS-HNNXBMFYSA-N

物化性质

• 沸点：
  388.9±25.0 °C(Predicted)
• 密度：
  0.924±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.93
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N-diisopropyl-2-(1-trimethylsilyl)ethylbenzamide 在 仲丁基锂 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 2.5h， 生成 (1RS,1'SR)-N,N-diisopropyl-2,6-bis-{(1-trimethylsilyl)ethyl}benzamide
  参考文献：
  名称：

  Conformational preference in aromatic amides bearing chiral ortho substituents: its origin and application to relayed stereocontrol

  摘要：

  具有立体中心的第三芳香酰胺在酰胺基团邻位可能采用两种不同的非对映异构体构象，这两种构象在环境温度下在核磁共振（NMR）时间尺度上缓慢互变，因此可通过NMR检测到。某些类型的立体中心，特别是亚磺酸盐、源自麻黄碱的噁唑啉和源自脯氨酸的咪唑啉，显著影响两种构象的分布。我们提出了一个模型，并通过分子力学计算支持该模型，合理化了根据控制中心的立体和电子特性所获得的构象选择性的方向和大小。对构象的控制可以通过将偏好的构象捕获为旋转异构体，或通过利用它来传递关于控制中心立体化学的信息来实现。

  DOI：

  10.1039/b514557k
• 作为产物：
  描述：

  二异己基酮 在 仲丁基锂 、 鹰爪豆碱 作用下， 以 四氢呋喃 、 环己烷 、 正戊烷 为溶剂， 反应 9.5h， 生成 N,N-diisopropyl-2-(1-trimethylsilyl)ethylbenzamide
  参考文献：
  名称：

  Atropisomeric Amides as Chiral Ligands:  Using (−)-Sparteine-Directed Enantioselective Silylation to Control the Conformation of a Stereogenic Axis

  摘要：

  An enantiomerically pure (1-trimethylsilyl)ethyl group, constructed by a (-)-sparteine-directed enantioselective quench of a laterally lithiated tertiary aromatic amide, exerts powerful thermodynamic control over the conformation of the adjacent tertiary amide substituent. Ortholithiation and functionalization of the amide in the 6-position allows the single amide conformer to be trapped as an enantiomerically and diastereoisomerically pure amide atropisomer. Protodesilylation of the amide gives functionalized atropisomeric amides with a stereogenic axis of single absolute configuration, whose barriers to racemization have been determined by polarimetry. Enantiomerically pure amides bearing phosphine substituents are effective ligands in a Pd-catalyzed allylic substitution reaction-the first use of a nonbiaryl atropisomer as a chiral ligand-and give products with 90% ee. The rate of racemization of the phosphine-substituted amide is powerfully influenced by the presence of palladium.

  DOI：

  10.1021/jo0007074

文献信息

• Two Different Pathways of Stereoinformation Transfer:  Asymmetric Substitutions in the (−)-Sparteine Mediated Reactions of Laterally Lithiated <i>N,N</i><i>-</i>Diisopropyl-<i>o</i>-ethylbenzamide and <i>N</i>-Pivaloyl-<i>o</i>-ethylaniline
  作者：S. Thayumanavan、Amit Basu、Peter Beak

  DOI：10.1021/ja970930r

  日期：1997.9.1

  Highly enantioenriched substitution products can be obtained by the (−)-sparteine mediated lithiation−substitution reactions of the laterally lithiated intermediates 3·1 and 14·1 derived from the amides 2 and 13. Either enantiomer of the products can be obtained with high enantioenrichment using (−)-sparteine as the ligand by appropriate choice of the protocol. The enantiodetermining step in both sequences

  由酰胺2和13衍生的横向锂化中间体3·1和14·1的(-)-sparteine介导的锂化-取代反应可以获得高度对映体富集的取代产物。产物的任一对映体都可以通过高对映体富集获得using (−)-sparteine as the ligand by appropriate choice of the protocol. 两个序列中的对映体决定步骤发生在去质子化之后。3·1 序列中的对映体富集来自动态动力学分辨率，而 14·1 序列中的对映体富集来自动态热力学分辨率。
• Asymmetric Substitutions: High and Opposite Enantioselective Alkylations of a Racemic Organolithium Intermediate in the Presence of (-)-Sparteine
  作者：S. Thayumanavan、Steven Lee、Chao Liu、Peter Beak

  DOI：10.1021/ja00100a053

  日期：1994.10
• Conformationally Interlocked Amides: Remote Asymmetric Induction by Mechanical Transfer of Stereochemical Information
  作者：Jonathan Clayden、Jennifer H Pink、Samreen A Yasin

  DOI：10.1016/s0040-4039(97)10443-9

  日期：1998.1

  The axial conformation of an aromatic tertiary amide group may be powerfully influenced by an adjacent stereogenic centre. Because the amide axis can also control the formation of new chiral centres, the amide can act as a "relay centre" for the transmission of stereochemical information. Conformational interlocking of adjacent amide groups on an aromatic ring means that a pair of amide groups can be used in series to mediate asymmetric induction between remote stereogenic centres, for example those lying para across an aromatic ring. (C) 1997 Elsevier Science Ltd. All rights reserved.
• Fluoride activated stereoinformation transfer from a CSi bond of a chiral benzyl silane to CC bonds
  作者：S. Thayumanavan、Yong Sun Park、Payman Farid、Peter Beak

  DOI：10.1016/s0040-4039(97)01214-8

  日期：1997.8

  Reactions of (S)-N, N-diisopropyl-o-(1'-trimethylsily)ethyl benzamide (1) with benzaldehyde, p-anisaldehyde, and acetophenone activated by fluoride provide diastereomers of N,N-diisopropyl-o-(2'-alkyl-2'-aryl-2'-hydroxy)ethyl benzamides 2, 3, and 4 with retention of configuration at the benzylic position in enantiomeric ratios of up to 90:10. Reactions of 1 with allyl bromide and allyl iodide in the presence of fluoride provides (R)-N,N-diisopropyl-o-(1'-methyl)but-3'-enylbenzamide (5) with modest enantiomeric ratios. The results are interpreted as involving collapse of a siliconate complex. (C) 1997 Elsevier Science Ltd.
• Conformational preference in aromatic amides bearing chiral ortho substituents: its origin and application to relayed stereocontrol
  作者：Mark S. Betson、Jonathan Clayden、Madeleine Helliwell、Paul Johnson、Lai Wah Lai、Jennifer H. Pink、Christopher C. Stimson、Neoclis Vassiliou、Neil Westlund、Samreen A. Yasin、Latifa H. Youssef

  DOI：10.1039/b514557k

  日期：——

  Tertiary aromatic amides bearing stereogenic centres ortho to the amide group may adopt two diastereoisomeric conformations which interconvert slowly on the NMR timescale at ambient temperature, and are therefore detectable by NMR. Certain classes of stereogenic centre—particularly sulfoxides, ephedrine-derived oxazolidines, and proline-derived imidazolidines—strongly bias the population of the two conformers. We propose a model, supported by molecular mechanics calculations, which rationalises the sense and magnitude of the conformational selectivity attained in terms of the steric and electronic properties of the controlling centre. The control over conformation may be exploited either by trapping the favoured conformer as an atropisomer, or by using it to relay information about the stereochemistry of the controlling centre.

  具有立体中心的第三芳香酰胺在酰胺基团邻位可能采用两种不同的非对映异构体构象，这两种构象在环境温度下在核磁共振（NMR）时间尺度上缓慢互变，因此可通过NMR检测到。某些类型的立体中心，特别是亚磺酸盐、源自麻黄碱的噁唑啉和源自脯氨酸的咪唑啉，显著影响两种构象的分布。我们提出了一个模型，并通过分子力学计算支持该模型，合理化了根据控制中心的立体和电子特性所获得的构象选择性的方向和大小。对构象的控制可以通过将偏好的构象捕获为旋转异构体，或通过利用它来传递关于控制中心立体化学的信息来实现。