2-(Dimethylphenylsilyl)benzaldehyd | 107116-07-4

• 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-(Dimethylphenylsilyl)benzaldehyd
• 英文别名: 2-[Dimethyl(phenyl)silyl]benzaldehyde
• CAS: 107116-07-4
• 化学式: C₁₅H₁₆OSi
• 分子量: 240.377
• InChiKey: MYJKICUWXGBFNI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.32
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(Dimethylphenylsilyl)benzaldehyd 在 bis(1,5-cyclooctadiene)nickel (0) 、 甲基锂 、 potassium hydroxide 、 sodium t-butanolate 、 (4R,5R)-1,3-bis-(2-isopropylphenyl)-4,5-diphenyl-4,5-dihydro-3H-imidazol-1-ium tetrafluoroborate 作用下， 以 四氢呋喃 、 乙醚 、 二甲基亚砜 、 甲苯 为溶剂， 反应 33.5h， 生成 (R)-orphenadrine
  参考文献：
  名称：

  Nickel(0)-Catalyzed Enantio- and Diastereoselective Synthesis of Benzoxasiloles: Ligand-Controlled Switching from Inter- to Intramolecular Aryl-Transfer Process

  摘要：

  A highly enantioselective synthesis of 3-aryl-, vinyl-, and alkynyl-2,1-benzoxasiloles (up to 99.9% ee and 99% yield) was achieved via the sequential activation of an aldehyde and a silane by nickel(0). This strategy was applied to a simultaneous generation of carbon- and silicon-stereogenic centers with excellent selectivity (dr = 99:1) via diastereotopic aryl transfer. Initial mechanistic studies revealed the complete switching of an aryl-transfer process from an intermolecular (racemic synthesis in the presence of IPr) to an intramolecular (enantioselective synthesis using chiral NHC, L5) fashion. A plausible rationale for the switching of the aryl-transfer process is given by a preliminary DFT calculation, which suggests that the coordination of 1 to the nickel(0)/L5 fragment in an eta(2)-arene:eta(2)-aldehyde fashion would be a key to the intramolecular process, while the formation of the corresponding intermediate is not possible in the presence of IPr. Owing to the chemically labile nature of its C-Si and O-Si bonds, enantioenriched benzoxasiloles are utilized for the synthesis of chiral building blocks and antihistaminic and anticholinergic drug molecules such as (R)-orphenadrine and (S)-neobenodine with no erosion of the enantiomeric excess.

  DOI：

  10.1021/jacs.5b07827
• 作为产物：
  描述：

  <2-(Dibrommethyl)phenyl>dimethylphenylsilan 在 水 、 calcium carbonate 作用下， 反应 18.0h， 以61%的产率得到2-(Dimethylphenylsilyl)benzaldehyd
  参考文献：
  名称：

  Wiese, Dietmar; Wannagat Ulrich; Thewalt, Ulf, Chemische Berichte, 1987, vol. 120, p. 873 - 878

  摘要：

  DOI：

文献信息

• N-CYCLOALKYL-N-[(TRISUBSTITUTEDSILYLPHENYL)METHYLENE]-(THIO)CARBOXAMIDE DERIVATIVES
  申请人：BAYER CROPSCIENCE

  公开号：US20150080337A1

  公开（公告）日：2015-03-19

  The present invention relates to fungicidal N-cycloalkyl-N-[(trisubstitutedsilylphenyl)methylene]carboxamide derivatives and their thiocarbonyl derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

  本发明涉及杀真菌的N-环烷基-N-[(三取代硅基苯基) 亚甲基]羧酰胺衍生物及其硫代氨基衍生物，其制备方法和制备中间体，其用作杀真菌剂，特别是以杀真菌剂组合物的形式和使用这些化合物或它们的组合物控制植物的植物病原真菌的方法。
• [EN] N-CYCLOALKYL-N-[(TRISUBSTITUTEDSILYLPHENYL)METHYLENE]-(THIO)CARBOXAMIDE DERIVATIVES<br/>[FR] DÉRIVÉS DE N-CYCLOALKYL-N-[(SILYLPHÉNYLE TRISUBSTITUÉ) MÉTHYLÈNE]-(THIO)CARBOXAMIDE
  申请人：BAYER CROPSCIENCE AG

  公开号：WO2013156560A1

  公开（公告）日：2013-10-24

  The present invention relates to fungicidal N-cycloalkyl-N-[(trisubstitutedsilylphenyl)methylene] carboxamide derivatives and their thiocarbonyl derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

  本发明涉及杀真菌的N-环烷基-N-[(三取代硅基苯基)亚甲基]羧酰胺衍生物及其硫代羰基衍生物，它们的制备方法和制备中间体化合物，它们作为杀真菌剂的用途，特别是以杀真菌剂组合物的形式，以及使用这些化合物或它们的组合物控制植物的植物病原真菌的方法。
• Highly Efficient Activation of Organosilanes with η²-Aldehyde Nickel Complexes: Key for Catalytic Syntheses of Aryl-, Vinyl-, and Alkynyl-Benzoxasiloles
  作者：Yoichi Hoshimoto、Hayato Yabuki、Ravindra Kumar、Haruka Suzuki、Masato Ohashi、Sensuke Ogoshi

  DOI：10.1021/ja510089c

  日期：2014.12.3

  An eta(2)-aldehyde nickel complex was utilized as an effective activator for an organosilane in order to generate a hypervalent silicate reactant for the first time. This method was successfully applied to the highly efficient syntheses of 3-aryl-, vinyl-, and alkynyl-2,1-benzoxasiloles from benzaldehydes with aryl-, vinyl-, and alkynylsilyl groups at the ortho position. Initial mechanistic studies revealed that an intermolecular aryl transfer process was involved in the reaction mechanism. The formation of an eta(2)-aldehyde complex was directly confirmed by NMR.
• Et-duphos-nickel-catalyzed asymmetric arylation of benzaldehyde derivatives bearing an ortho-Me2PhSi group with potassium aryltriolborates
  作者：Fumie Sakurai、Kazuhiro Kondo、Toyohiko Aoyama

  DOI：10.1016/j.tetlet.2009.08.019

  日期：2009.11

  The Ni-catalyzed asymmetric arylation of benzaldehydes bearing an ortho-masked H group with potassium aryltriolborates has been developed. The keys to success were (i) steric tuning of benzaldehyde derivatives with an ortho-Me2PhSi group, and (ii) the use of potassium aryltriolborates as aryl sources. (C) 2009 Elsevier Ltd. All rights reserved.
• WIESE D.; WANNAGAT U.; THEWALT U.; DEBAERDEMAEKER T., CHEM. BER., 120,(1987) N 6, 873-878
  作者：WIESE D.、 WANNAGAT U.、 THEWALT U.、 DEBAERDEMAEKER T.

  DOI：——

  日期：——