(S)-N-{1-[(diphenylphosphanyl)-methyl]-2-methyl-propyl}-N-methyl-benzamide | 354112-89-3

• 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: (S)-N-{1-[(diphenylphosphanyl)-methyl]-2-methyl-propyl}-N-methyl-benzamide
• 英文别名: (S)-N-iso-propyl-2-amino-3-methylbutyl-1-diphenylphosphine；(S)-2-isopropylamino-3-methyl-1-(diphenylphosphino)butane；(2S)-1-diphenylphosphanyl-3-methyl-N-propan-2-ylbutan-2-amine
• CAS: 354112-89-3
• 化学式: C₂₀H₂₈NP
• 分子量: 313.423
• InChiKey: MNFQKKJREXDZLJ-HXUWFJFHSA-N

物化性质

• 沸点：
  406.0±28.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-N-{1-[(diphenylphosphanyl)-methyl]-2-methyl-propyl}-N-methyl-benzamide 在 [(6)Li]-n-butyllithium 作用下， 以 氘代四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  配位溶剂中手性N，P-酰胺配体的聚集和溶剂化：计算和NMR光谱研究

  摘要：

  在溶液中研究了一系列手性N，P配体的锂酰胺。先前已证明该配体类别在苯甲醛的不对称烷基化中具有良好的选择性。发现这些酰胺酰胺聚集成二聚体，磷与锂的配位力出乎意料地强。发现二聚体形式之间的平衡在很大程度上取决于溶质内部以及溶质与溶剂之间的非键相互作用。只有将分散度和自由能的贡献比例定为气相值的约20％，才有可能重现实验观察到的聚集偏好。计算了NMR光谱屏蔽物，发现其与实验观察到的位移有很好的相关性。计算得出的Li，P耦合是对Li的敏感度量。P距离。

  DOI：

  10.1002/cplu.201200033
• 作为产物：
  描述：

  (1S)-[1-[(diphenylphosphino)methyl]-2-methylpropyl]carbamic acid 1,1-dimethylethyl ester 在 aluminum oxide 、 lithium aluminium tetrahydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 28.0h， 生成 (S)-N-{1-[(diphenylphosphanyl)-methyl]-2-methyl-propyl}-N-methyl-benzamide
  参考文献：
  名称：

  Investigation of the importance of nitrogen substituents in a N–P chiral ligand for enantioselective allylic alkylation

  摘要：

  The synthesis of three chiral chelate nitrogen-phosphorus (S)-valine derived ligands with the potential fur stereogenic nitrogen donation is described. In palladium catalysed allylic substitution reactions the ligands induced varying enantioselectivities ranging From 92%, e.e. of the (R)-enantiomer to 83% e.e. of the (S)-enantiomer. Structural and spectroscopic investigations into the origin of this effect were conducted, but were inconclusive. However, the importance of the consideration of N-substituents in such systems is highlighted. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00137-9

文献信息

• A long-range chiral relay via tertiary amide group in asymmetric catalysis: new amino acid-derived N,P-ligands for copper-catalysed conjugate addition
  作者：Andrei V. Malkov、John B. Hand、Pavel Kočovský

  DOI：10.1039/b304131j

  日期：——

  New N,P-ligands 4-6, derived from valinol and prolinol, respectively, have been developed for the asymmetric, copper(I)-catalysed conjugate addition of diethylzinc to unsaturated ketones; the tertiary amide group has been shown to effectively relay the chiral information from the ligand backbone to the active centre.

  已经开发出分别衍生自缬氨醇和脯氨醇的新的N，P-配体4-6，用于不饱和酮的铜（I）催化的不对称铜（I）共轭加成反应。已经显示叔酰胺基团有效地将手性信息从配体主链传递至活性中心。
• Improved and Efficient Synthesis of Chiral N,P-Ligands via Cyclic Sulfamidates for Asymmetric Addition of Butyllithium to Benzaldehyde
  作者：Petra Rönnholm、Mikael Södergren、Göran Hilmersson

  DOI：10.1021/ol701504c

  日期：2007.9.1

  scaleable route to chiral 1-isopropylamino-2-(diphenylphosphino)ethanes is described via the ring-opening of chiral, cyclic sulfamidates with potassium diphenylphosphide (KPPh(2)). The novel protocol offers a robust access to gram quantities of chiral amino phosphinoethanes in high yields. The Li-amides of the chiral aminophosphines were evaluated as chiral ligands in the asymmetric addition of n-butyllithium

  通过手性环状氨基磺酸盐与二苯基磷化钾（KPPh（2））的开环，描述了一种制备手性1-异丙基氨基-2-（二苯基膦基）乙烷的稳健且可扩展的途径。该新颖的方案提供了以高收率可靠地获得克量的手性氨基膦基乙烷的方法。在将正丁基锂（BuLi）不对称加成到苯甲醛中时，手性氨基膦的Li-酰胺被评价为手性配体，可生成1-98％ee的1-苯基戊醇。
• Investigation of the importance of nitrogen substituents in a N–P chiral ligand for enantioselective allylic alkylation
  作者：James C. Anderson、Rachel J. Cubbon、John D. Harling

  DOI：10.1016/s0957-4166(01)00137-9

  日期：2001.4

  The synthesis of three chiral chelate nitrogen-phosphorus (S)-valine derived ligands with the potential fur stereogenic nitrogen donation is described. In palladium catalysed allylic substitution reactions the ligands induced varying enantioselectivities ranging From 92%, e.e. of the (R)-enantiomer to 83% e.e. of the (S)-enantiomer. Structural and spectroscopic investigations into the origin of this effect were conducted, but were inconclusive. However, the importance of the consideration of N-substituents in such systems is highlighted. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Aggregation and Solvation of Chiral N,P-Amide Ligands in Coordinating Solvents: A Computational and NMR Spectroscopic Study
  作者：Petra Rönnholm、Sten O. Nilsson Lill、Jürgen Gräfenstein、Per-Ola Norrby、Mariell Pettersson、Göran Hilmersson

  DOI：10.1002/cplu.201200033

  日期：2012.9

  The lithium amides of a series of chiral N,P ligands were studied in solution. This ligand class had been shown previously to give good selectivities in asymmetric alkylation of benzaldehyde. These lithium amides were found to aggregate into dimers with surprisingly strong coordination of phosphorus to lithium. The equilibrium between dimeric forms was found to depend strongly on non‐bonded interactions

  在溶液中研究了一系列手性N，P配体的锂酰胺。先前已证明该配体类别在苯甲醛的不对称烷基化中具有良好的选择性。发现这些酰胺酰胺聚集成二聚体，磷与锂的配位力出乎意料地强。发现二聚体形式之间的平衡在很大程度上取决于溶质内部以及溶质与溶剂之间的非键相互作用。只有将分散度和自由能的贡献比例定为气相值的约20％，才有可能重现实验观察到的聚集偏好。计算了NMR光谱屏蔽物，发现其与实验观察到的位移有很好的相关性。计算得出的Li，P耦合是对Li的敏感度量。P距离。