N-((dimethyl(phenyl)silyl)(phenyl)methyl)-p-toluenesulfonamide | 1586870-04-3

• 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-((dimethyl(phenyl)silyl)(phenyl)methyl)-p-toluenesulfonamide
• 英文别名: (S)-N-{[dimethyl(phenyl)silyl](phenyl)methyl}-4-toluenesulfonamide；(S)-4-methyl-N-(2-methyl-1,2-diphenylpropyl)benzenesulfonamide；N-[(S)-[dimethyl(phenyl)silyl]-phenylmethyl]-4-methylbenzenesulfonamide
• CAS: 1586870-04-3
• 化学式: C₂₂H₂₅NO₂SSi
• 分子量: 395.598
• InChiKey: HZXHHQCUYCTPOR-QFIPXVFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  46.17
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  (S,S)-N-{[dimethyl(phenyl)silyl](phenyl)methyl}-4-toluenesulfinamide 以 二氯甲烷 为溶剂， 以80%的产率得到N-((dimethyl(phenyl)silyl)(phenyl)methyl)-p-toluenesulfonamide
  参考文献：
  名称：

  使用预先形成的NHC-Copper（I）配合物作为催化剂，将硅亲核试剂与醛亚胺进行对映选择性加成反应

  摘要：

  解决了将硅亲核试剂不对称添加到典型的手性受体中的另一个主要挑战，即对醛亚胺的对映选择性1,2-加成。在Si的活化在硅pronucleophile乙键通过与麦奎德的手性六元N-杂环卡宾作为支撑配体释放硅亲核体，这增加了具有高水平的对映选择性的各种醛亚胺铜（I）醇盐。新方法提供了催化不对称地接触α-甲硅烷基化胺的方法。

  DOI：

  10.1002/anie.201402086

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）。
• Enantioselective Synthesis of α-Silylamines by Meerwein–Ponndorf–Verley-Type Reduction of α-Silylimines by a Chiral Lithium Amide
  作者：Yasuhiro Kondo、Michiko Sasaki、Masatoshi Kawahata、Kentaro Yamaguchi、Kei Takeda

  DOI：10.1021/jo500441a

  日期：2014.4.18

  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.
• Synthesis of [2.2]paracyclophane-based bidentate oxazoline–carbene ligands for the asymmetric 1,2-silylation of N -tosylaldimines
  作者：Xichao Wang、Zhen Chen、Wenzeng Duan、Chun Song、Yudao Ma

  DOI：10.1016/j.tetasy.2017.05.001

  日期：2017.6

  A series of novel oxazoline-substituted imidazolium salts with planar and central chirality has been successfully synthesized and applied to copper-catalyzed enantioselective 1,2-silylation of N-tosylaldimines. The oxazoline-carbene copper complex generated in situ by the reaction of the oxazoline-substituted imidazolium and Cu2O demonstrated an exceptionally high catalytic activity in the asymmetric 1,2-silylation of N-tosylaldimines, affording chiral alpha-amino silanes with excellent yields and enantioselectivities. (C) 2017 Elsevier Ltd. All rights reserved.