3,3-dimethyl-2-phenylbutanal | 86429-26-7

• 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: 3,3-dimethyl-2-phenylbutanal
• CAS: 86429-26-7
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: RUTMKMJJXILHCZ-UHFFFAOYSA-N

物化性质

• 沸点：
  247.6±9.0 °C(Predicted)
• 密度：
  0.945±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  3,3-dimethyl-2-phenylbutanal 在 silver hexafluoroantimonate 、 silver(I) bifluoride 、 [RuCl₂((1S,2S)-N,N'-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine)] 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以13%的产率得到2-fluoro-3,3-dimethyl-2-phenylbutyraldehyde
  参考文献：
  名称：

  Asymmetric oxidative α-fluorination of 2-alkylphenylacetaldehydes with AgHF2 and ruthenium/PNNP catalysts

  摘要：

  During attempts directed at epoxide ring opening with different HF sources, we discovered that the Lewis acidic [RuCl(PNNP)](+) (1) or [Ru(OEt2)(2)(PNNP)](2+) (2) catalysts promote the [1,2]-phenyl shift (Meinwald rearrangement) in phenyl-substituted epoxides to give the corresponding 2-alkylphenylacetaldehydes, which are fluorinated at the alpha-position in the presence of silver bifluoride (AgHF2) (PNNP is (1S,2S)-N,N'-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine). The optimization of aldehyde fluorination with PhCH(R)CHO (R = Me, Et, Pr-i, Bu-t) as substrates showed that catalyst [1]SbF6 gives a moderate degree of enantioselectivity (up to 27% ee) and 35% yield. The substrate scope is limited to benzylic aldehydes. The reaction is unprecedented for transition metal catalysts. Circumstantial evidence suggests that the mechanism involves chemical oxidation followed by enantioselective fluorination with F-. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2009.05.008
• 作为产物：
  描述：

  (1-叔丁基乙烯基)苯 生成 3,3-dimethyl-2-phenylbutanal
  参考文献：
  名称：

  Analyse conformationnelle en serie allenique oxydes de phosphine diphenyles alleniques

  摘要：

  DOI：

  10.1016/0040-4020(72)88116-x

文献信息

• Ba(OH)2 as catalyst in organic reactions
  作者：J.V. Sinisterra、J.M. Marinas、F. Riquelme、M.S. Arias

  DOI：10.1016/s0040-4020(01)85922-6

  日期：1988.1

  The reactivity of several products R1R2CH-X+,1, (X=N,P,S), which can produce ylids by reaction with bases, has been tested using the activated barium hydroxide catalysts, C-200. Wittig-Horner, Wittig, Corey-Chaykovsky and Kröhnke type reactions have been analyzed. The pKa of 1, and the structure of active sites control the process. When 1 has a strong acid character, the process takes place -dissolving

  已使用活化的氢氧化钡催化剂C-200测试了几种产物R 1 R 2 CH-X +，1（X = N，P，S）的反应性，这些产物可通过与碱反应生成碘。对Wittig-Horner，Wittig，Corey-Chaykovsky和Kröhnke型反应进行了分析。pKa为1，以及活性位点的结构控制着这一过程。当1具有强酸特性时，将发生过程-将固体溶解-形成均相。当1的pKa值<11时，该过程在固体的强碱位置（pKa> 11.7）进行，该位点控制了反应机理和吸附的类固醇的反应性。
• An air-stable cationic iridium hydride as a highly active and general catalyst for the isomerization of terminal epoxides
  作者：Nicolas Humbert、Devendra J. Vyas、Céline Besnard、Clément Mazet

  DOI：10.1039/c4cc05260a

  日期：——

  We describe the use of an air-stable iridium hydride catalyst for the isomerization of terminal epoxides into aldehydes with perfect regioselectivity.

  我们描述了使用一种空气稳定的铱氢化物催化剂将末端环氧化物异构化为具有完美区域选择性的醛的方法。
• Acyclic stereoselection. 40. Steric effects, as well as .sigma.*-orbital energies, are important in diastereoface differentiation in additions to chiral aldehydes
  作者：Eric P. Lodge、Clayton H. Heathcock

  DOI：10.1021/ja00245a027

  日期：1987.5

  Etude des reactions d'aldolisation de deux series d'aldehydes chiraux avec l'enolate de lithium de la pinacolone

  练习曲 d'aldolisation de deux series d'aldehydes chiraux avec l'enolate delithium de la pinacolone
• Complementary Catalytic Strategies to Access ?-Chiral Aldehydes
  作者：Clément Mazet

  DOI：10.2533/chimia.2013.658

  日期：——

  The present article summarizes the development of two novel and complementary catalytic methods to access ?-chiral aldehydes. A C1-symmetric chiral (P,N) ligand with a structure derived from the ubiquitous binepine scaffold has been specifically designed for the Pd-catalyzed ?-arylation of aldehydes to access indane derivatives with a well-defined quaternary stereocenter in high yields and excellent enantioselectivities. In addition, a dinuclear palladium hydride catalyst has been synthesized for the isomerization of terminal and trisubstituted epoxides into aldehydes and ketones respectively. Combined experimental and theoretical investigations pointed to an unprecedented 'epoxide-opening/hydride-transfer' sequence. The mechanism also features two distinct enantio-determining steps in the kinetic resolution of racemic epoxides.

  本文总结了两种新颖且互补的催化方法的发展，用于获取α-手性醛类化合物。一种源自广泛存在的bipine桥架的C1对称手性（P,N）配体已经专门设计用于Pd催化的α-芳基化反应，以获得具有明确定义的四元手性中心的茚烷衍生物，产率高且选择性优异。此外，合成了一种双核钯氢化物催化剂，用于将末端和三取代环氧化物异构化为相应的醛和酮。结合实验和理论研究指出了一种前所未有的“环氧化物开环/氢转移”序列。该机制还包括在消旋环氧化物的动力学拆分过程中的两个不同的手性决定步骤。
• An efficient and stereoselective Wittig–Horner synthesis of acyclic α-enones with barium hydroxide as solid catalyst
  作者：Carlos Alvarez-Ibarra、Selma Arias、Gabriel Bañón、María J. Fernández、Miguel Rodríguez、Vicente Sinisterra

  DOI：10.1039/c39870001509

  日期：——

  Wittig–Horner reactions under interfacial solid–liquid conditions using activated barium hydroxide catalyst C-200 produce acyclic α-enones with high yields and selectivities.

  使用活化的氢氧化钡催化剂C-200在界面固液条件下进行的Wittig-Horner反应产生了高产率和高选择性的无环α-烯酮。