2-(dimethyl(phenyl)silyl)-5-fluorobenzaldehyde | 1196117-41-5

• 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-(dimethyl(phenyl)silyl)-5-fluorobenzaldehyde
• 英文别名: 2-[Dimethyl(phenyl)silyl]-5-fluorobenzaldehyde；2-[dimethyl(phenyl)silyl]-5-fluorobenzaldehyde
• CAS: 1196117-41-5
• 化学式: C₁₅H₁₅FOSi
• 分子量: 258.367
• InChiKey: NTLYFJMUPFZYLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.46
• 重原子数：
  18
• 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：
  2

反应信息

• 作为反应物：
  描述：

  2-(dimethyl(phenyl)silyl)-5-fluorobenzaldehyde 在 bis(1,5-cyclooctadiene)nickel (0) 、 四丁基氟化铵 、 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 、 甲苯 为溶剂， 反应 3.0h， 生成 (R)-(3-fluorophenyl)(phenyl)methanol
  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-溴-5-氟苯甲醛 、 苯基二甲基氯硅烷 在 对甲苯磺酸 、 正丁基锂 作用下， 以 乙醇 、 乙醚 、 正己烷 为溶剂， 反应 22.0h， 生成 2-(dimethyl(phenyl)silyl)-5-fluorobenzaldehyde
  参考文献：
  名称：

  Et-duphos-nickel-catalyzed asymmetric arylation of benzaldehyde derivatives bearing an ortho-Me2PhSi group with potassium aryltriolborates

  摘要：

  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.

  DOI：

  10.1016/j.tetlet.2009.08.019

文献信息

• Nickel(0)-Catalyzed Enantio- and Diastereoselective Synthesis of Benzoxasiloles: Ligand-Controlled Switching from Inter- to Intramolecular Aryl-Transfer Process
  作者：Ravindra Kumar、Yoichi Hoshimoto、Hayato Yabuki、Masato Ohashi、Sensuke Ogoshi

  DOI：10.1021/jacs.5b07827

  日期：2015.9.16

  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.
• 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.