N-(phenyl(trimethylsilyl)methyl)-p-toluenesulfonamide | 1586870-02-1

• 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-(phenyl(trimethylsilyl)methyl)-p-toluenesulfonamide
• 英文别名: (S)-4-methyl-N-(phenyl(trimethylsilyl)methyl)benzenesulfonamide；4-methyl-N-[(S)-phenyl(trimethylsilyl)methyl]benzenesulfonamide
• CAS: 1586870-02-1
• 化学式: C₁₇H₂₃NO₂SSi
• 分子量: 333.527
• InChiKey: FDNZEXYZEXCXEH-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.89
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  54.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  N-(phenyl(trimethylsilyl)methylene)-p-toluenesulfonamide 在 正丁基锂 、 (S)-2,2-dimethyl-N-(2-(4-methylpiperazin-1-yl)-1-phenylethyl)propan-1-amine 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 以58%的产率得到N-(phenyl(trimethylsilyl)methyl)-p-toluenesulfonamide
  参考文献：
  名称：

  Enantioselective Synthesis of α-Silylamines by Meerwein–Ponndorf–Verley-Type Reduction of α-Silylimines by a Chiral Lithium Amide

  摘要：

  Meerwein-Ponndorf-Verley-type reduction of N-tosylsilylimines with chiral lithium amide 2 affords alpha-silylamines in high enantioselectivity. Since the enantioselectivity observed was inconsistent with our previously proposed chairlike six-membered transition structure, we performed density functional theory (DFT) calculations on transition states leading to (S)- and (R)-7a and (S)- and (R)-7e using an N-phenylsulfonyl derivatives 12 and 13 as model systems. Results of the calculations showed that the structures are considerably deformed from the chairlike form with steric repulsions between the 1'-methylene group and the imine-carbon substituents playing an important role in the control of the, enantioselectivity.

  DOI：

  10.1021/jo500441a

文献信息

• Synthesis of Chiral α-Aminosilanes through Palladium-Catalyzed Asymmetric Hydrogenation of Silylimines
  作者：Dongyang Fan、Yang Liu、Jia Jia、Zhenfeng Zhang、Yangang Liu、Wanbin Zhang

  DOI：10.1021/acs.orglett.8b04073

  日期：2019.2.15

  The asymmetric hydrogenation of silylimines was first developed by using a palladium complex of a P-stereogenic diphosphine ligand as the catalyst, affording the valuable chiral α-aminosilanes with quantitative conversions and excellent enantioselectivities (up to 99% ee).

  甲硅烷基丙氨酸的不对称氢化首先通过使用P-立体异构二膦配体的钯配合物作为催化剂来开发，从而提供了有价值的手性α-氨基硅烷，具有定量转化率和出色的对映选择性（高达99％ee）。