(S)-N,N-diisopropyl-2-(1-trimethylsilylethyl)-6-diphenylphosphonylbenzamide

• 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: (S)-N,N-diisopropyl-2-(1-trimethylsilylethyl)-6-diphenylphosphonylbenzamide
• 英文别名: 2-diphenylphosphoryl-N,N-di(propan-2-yl)-6-[(1S)-1-trimethylsilylethyl]benzamide
• 化学式: C₃₀H₄₀NO₂PSi
• 分子量: 505.712
• InChiKey: WLNLSHGVCZBHPR-DEOSSOPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.57
• 重原子数：
  35
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-N,N-diisopropyl-2-(1-trimethylsilylethyl)-6-diphenylphosphonylbenzamide 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 以99%的产率得到N,N-diisopropyl-2-ethyl-6-diphenylphosphonylbenzamide
  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
• 作为产物：
  描述：

  N,N-diisopropyl-2-ethylbenzamide 在 仲丁基锂 、 鹰爪豆碱 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 9.0h， 生成 (S)-N,N-diisopropyl-2-(1-trimethylsilylethyl)-6-diphenylphosphonylbenzamide
  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

• Atropisomeric Amides as Chiral Ligands:  Using (−)-Sparteine-Directed Enantioselective Silylation to Control the Conformation of a Stereogenic Axis
  作者：Jonathan Clayden、Paul Johnson、Jennifer H. Pink、Madeleine Helliwell

  DOI：10.1021/jo0007074

  日期：2000.10.1

  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.