2-trimethylsilyloxy-2-(2-bromophenyl)acetonitrile | 1005005-10-6

• 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: 2-trimethylsilyloxy-2-(2-bromophenyl)acetonitrile
• 英文别名: (2S)-2-(2-bromophenyl)-2-trimethylsilyloxyacetonitrile
• CAS: 1005005-10-6
• 化学式: C₁₁H₁₄BrNOSi
• 分子量: 284.228
• InChiKey: DWMHMTAUBSJDPQ-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.87
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  三甲基氰硅烷 、 邻溴苯甲醛 在 titanium(IV) isopropylate 、 (1R,2S,3R,4S)-3-((E)-(2-hydroxy-3-isopropylbenzylidene)amino)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以34%的产率得到
  参考文献：
  名称：

  由新颖樟脑催化醛的对映选择性硅氰化反应衍生的席夫碱 - 钛（IV）配合物

  摘要：

  五三齿席夫碱已经从（1制备- [R，2小号，3 - [R，4小号）-3-氨基- 1,7,7-三甲基二环[2.2.1]庚-2-醇和水杨醛。X射线结构的调查显示在它们的分子构象的差异，和它们的钛（IV）络合物进行了研究NMR技术。它们之间的复合物与由2-羟基-3-异丙基苯甲醛得到的席夫碱，为脂肪族，脂环族，芳族，杂芳族和醛的硅氰化反应最有选择性的催化剂。最高的对映选择性，> 99％时，在加入三甲基氰硅烷的给肉桂醛实现。

  DOI：

  10.1016/j.tetasy.2014.03.001

文献信息

• Fine Modification of Salen Ligands - Effects on the Salen-Ti-Catalyzed Asymmetric Cyanosilylation of Aldehydes
  作者：Chengwei Lv、Qigan Cheng、Daqian Xu、Shoufeng Wang、Chungu Xia、Wei Sun

  DOI：10.1002/ejoc.201100319

  日期：2011.7

  bifunctional N-oxide salen―Ti IV complexes and a pyrrolidine salen―Ti IV complex in combination with achiral N-oxide were developed and applied to the asymmetric addition of trimethylsilyl cyanide to aldehydes. Notably, both enantiomers of trimethylsilyl ethers of cyanohydrins could be easily prepared by modifying the catalysts employed in this reaction, which are based on the same chiral diamine collar

  开发了新的双功能 N-氧化物 salen-Ti IV 配合物和吡咯烷 salen-Ti IV 配合物与非手性 N-氧化物的结合，并将其应用于三甲基氰基氰化物与醛的不对称加成。值得注意的是，氰醇的三甲基甲硅烷基醚的两种对映异构体都可以通过修改该反应中使用的催化剂来轻松制备，这些催化剂基于相同的手性二胺环，源自 L-酒石酸。通过使用相对低的催化剂负载量和仅 1.05 当量的三甲基氰基氰化物 (TMSCN)，通常以中等至良好的对映体过量和优异的产率获得产物。
• A practical Ti-salen catalyst based on dimeric salen ligand for asymmetric addition of trimethylsilyl cyanide to aldehydes
  作者：Chengwei Lv、Daqian Xu、Shoufeng Wang、Cheng-Xia Miao、Chungu Xia、Wei Sun

  DOI：10.1016/j.catcom.2011.04.022

  日期：2011.7

  from L-tartaric acid was synthesized through linking two salen units with 1,6-dibromohexane. The corresponding Ti complex was proved to be an efficient catalyst for asymmetric addition of trimethylsilyl cyanide to aldehydes, providing the corresponding optically active trimethylsilyl ether of cyanohydrins with moderate to good enantiomeric excesses and excellent yields under relatively low catalyst

  通过将两个salen单元与1,6-二溴己烷连接，合成了衍生自L-酒石酸的二聚salen配体。事实证明，相应的Ti络合物是将三甲基甲硅烷基氰化物不对称加成到醛中的有效催化剂，在相对较低的催化剂负载条件下，提供了相应的旋光性的氰醇三甲基甲硅烷基醚，具有中等至良好的对映体过量，且产率高。
• Enantioselective cyanosilylation of aldehydes catalyzed by a multistereogenic salen–Mn(<scp>iii</scp>) complex with a rotatable benzylic group as a helping hand
  作者：Yun-Long Wei、Wei-Sheng Huang、Yu-Ming Cui、Ke-Fang Yang、Zheng Xu、Li-Wen Xu

  DOI：10.1039/c4ra12884b

  日期：——

  A multistereogenic salen–Mn(iii) complex bearing an aromatic pocket and two benzylic groups as helping hands was found to be efficient in the catalysis of asymmetric cyanosilylation.

  一种具有芳香口袋和两个苄基辅助作用的多手性salen-Mn（III）配合物被发现在不对称氰基硅化反应中具有高效催化作用。
• Enantioselective cyanation of aldehydes catalyzed by bifunctional salen–aluminum complex
  作者：Chengwei Lv、Cheng-Xia Miao、Daqian Xu、Shoufeng Wang、Chungu Xia、Wei Sun

  DOI：10.1016/j.catcom.2012.06.025

  日期：2012.10

  Chiral N-oxide salen ligands and their corresponding Al complexes were synthesized. Notably, the catalytic activity and asymmetric induction ability of the bifunctional N-oxide salen-Al for asymmetric cyanosilylation were compared with that of bi-component catalyst system including chiral pyrrolidine salen-Al complex and Ph3PO. Interestingly, introducing N-oxide group in salen unit could enhance the activity and enantioselectivity of bifunctional catalyst without further adding Ph3PO as co-catalyst and inverse configurations were generated from the two systems. In addition, excellent yields and high ee values could be obtained under milder conditions in bifunctional catalyst system compared with that of bi-component catalyst system. (C) 2012 Elsevier B.V. All rights reserved.
• Synthesis, characterization and catalytic property of chiral oxo-vanadium (+)-pseudoephedrine complex supported on magnetic nanoparticles Fe3O4 in the cyanosilylation of carbonyl compounds
  作者：Amin Rostami、Bahareh Atashkar

  DOI：10.1016/j.catcom.2014.08.029

  日期：2015.1

  Vanadium complex of pseudoephedrine immobilized on magnetic nanoparticle Fe3O4(Pseudoephedrine) @MNPs] was prepared and characterized by UV-vis, SEM, XRD, TGA, EDX, FT-IR, AGFM and elemental analysis techniques. VO(Pseudoephedrine)@MNPs was found to catalyze the cyanosilylation of carbonyl compounds using TMSCN in good yields with 8-25% enantiomeric excesses under solvent-free conditions at room temperature. The catalyst was recycled up to 15 times with little loss of activity and enantioselectivity. (C) 2014 Elsevier B.V. All rights reserved.