(R)-3-(dimethyl(phenyl)silyl)-3-phenylpropanenitrile

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (R)-3-(dimethyl(phenyl)silyl)-3-phenylpropanenitrile
• 英文别名: (3R)-3-[dimethyl(phenyl)silyl]-3-phenylpropanenitrile
• 化学式: C₁₇H₁₉NSi
• 分子量: 265.43
• InChiKey: GIRFIJMWKJZYTI-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (肉)桂腈 、 (二甲基苯硅烷基)硼酸频那醇酯 在 C₂₀H₂₈N₂O₂*Cu⁽²⁺⁾*2C₅H₇O₂^(1-) 作用下， 以 水 为溶剂， 反应 48.0h， 以78%的产率得到(R)-3-(dimethyl(phenyl)silyl)-3-phenylpropanenitrile
  参考文献：
  名称：

  An Insoluble Copper(II) Acetylacetonate–Chiral Bipyridine Complex that Catalyzes Asymmetric Silyl Conjugate Addition in Water

  摘要：

  Acicular purplish crystals were obtained from Cu(acac)(2) and a chiral bipyridine ligand. Although the crystals were not soluble, they nevertheless catalyzed asymmetric silyl conjugate addition of lip ophilic substrates in water. Indeed, the reactions proceeded efficiently only in water; they did not proceed well either in organic solvents or in mixed water/organic solvents in which the catalyst/substrates were soluble. This is in pronounced contrast to conventional organic reactions wherein the catalyst/substrates tend to be in solution. Several advantages of the chiral Cu(II) catalysis in water over previously reported catalyst systems have been demonstrated. Water is expected to play a prominent role in constructing and stabilizing sterically confined transition states and accelerating subsequent protonation to achieve high yields and enantioselectivities.

  DOI：

  10.1021/jacs.5b11418

文献信息

• Enantioselective Conjugate Silyl Additions to Cyclic and Acyclic Unsaturated Carbonyls Catalyzed by Cu Complexes of Chiral N-Heterocyclic Carbenes
  作者：Kang-sang Lee、Amir H. Hoveyda

  DOI：10.1021/ja910989n

  日期：2010.3.10

  Cu-catalyzed enantioselective conjugate additions proceed to completion within only 2 h to afford the desired silanes in 87-97% yield and 90:10-99:1 enantiomeric ratio (er). Use of a proton source (e.g., MeOH) is not required; accordingly, synthetically versatile alpha-silyl boron enolates can be obtained. The special utility of the present protocol, in comparison with the related catalytic enantioselective

  公开了一种有效的铜催化方案，用于将二甲基苯基硅烷基对映选择性加成到范围广泛的环状和非环状不饱和酮、酯、丙烯腈和 α、β、γ、δ-二烯酮。反应在 1-2 mol% 的市售且廉价的 CuCl、一种易于获得的单齿咪唑啉盐和市售的（二甲基苯基甲硅烷基）频哪醇硼存在下进行。铜催化的对映选择性共轭添加仅在 2 小时内完成，以 87-97% 的产率和 90:10-99:1 的对映体比率 (er) 提供所需的硅烷。不需要使用质子源（例如，MeOH）；因此，可以获得合成通用的α-甲硅烷基硼烯醇化物。本协议的特殊用途，
• An Insoluble Copper(II) Acetylacetonate–Chiral Bipyridine Complex that Catalyzes Asymmetric Silyl Conjugate Addition in Water
  作者：Taku Kitanosono、Lei Zhu、Chang Liu、Pengyu Xu、Shu̅ Kobayashi

  DOI：10.1021/jacs.5b11418

  日期：2015.12.16

  Acicular purplish crystals were obtained from Cu(acac)(2) and a chiral bipyridine ligand. Although the crystals were not soluble, they nevertheless catalyzed asymmetric silyl conjugate addition of lip ophilic substrates in water. Indeed, the reactions proceeded efficiently only in water; they did not proceed well either in organic solvents or in mixed water/organic solvents in which the catalyst/substrates were soluble. This is in pronounced contrast to conventional organic reactions wherein the catalyst/substrates tend to be in solution. Several advantages of the chiral Cu(II) catalysis in water over previously reported catalyst systems have been demonstrated. Water is expected to play a prominent role in constructing and stabilizing sterically confined transition states and accelerating subsequent protonation to achieve high yields and enantioselectivities.