(S)-4,4-dimethyl-3-phenylpentanal | 137623-80-4

• 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: (S)-4,4-dimethyl-3-phenylpentanal
• 英文别名: (3S)-4,4-dimethyl-3-phenylpentanal
• CAS: 137623-80-4
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: QYANNNAENAUKBY-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  (S)-4,4-dimethyl-3-phenylpentanal 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 0.25h， 生成 (S)-4,4-dimethyl-3-phenylpentan-1-ol
  参考文献：
  名称：

  Asymmetric Michael additions to .alpha.,.beta.-unsaturated oxazolines. An efficient preparation of chiral .beta.,.beta.-disubstituted propionaldehydes

  摘要：

  A short stereoselective route to a variety of chiral, nonracemic alpha,beta-unsaturated oxazolines derived from (S)-tert-leucinol is described. Addition of organolithium reagents to this chiral oxazoline occurs in a Michael fashion, giving rise to adducts with high diastereoselectivity. Reductive cleavage of the oxazoline leaves the beta,beta-disubstituted aldehydes in > 93% ee. This process represents a significant improvement in one of the earliest asymmetric conjugate additions first reported in 1975.

  DOI：

  10.1021/jo00025a027
• 作为产物：
  描述：

  (4S)-4-tert-butyl-2-((E)-2-phenylethenyl)-2-oxazoline 以 四氢呋喃 为溶剂， 生成 (S)-4,4-dimethyl-3-phenylpentanal
  参考文献：
  名称：

  Asymmetric Michael additions to .alpha.,.beta.-unsaturated oxazolines. An efficient preparation of chiral .beta.,.beta.-disubstituted propionaldehydes

  摘要：

  A short stereoselective route to a variety of chiral, nonracemic alpha,beta-unsaturated oxazolines derived from (S)-tert-leucinol is described. Addition of organolithium reagents to this chiral oxazoline occurs in a Michael fashion, giving rise to adducts with high diastereoselectivity. Reductive cleavage of the oxazoline leaves the beta,beta-disubstituted aldehydes in > 93% ee. This process represents a significant improvement in one of the earliest asymmetric conjugate additions first reported in 1975.

  DOI：

  10.1021/jo00025a027

文献信息

• Direct Stereoselective Installation of Alkyl Fragments at the β-Carbon of Enals via Excited Iminium Ion Catalysis
  作者：Charlie Verrier、Nurtalya Alandini、Cristofer Pezzetta、Mauro Moliterno、Luca Buzzetti、Hamish B. Hepburn、Alberto Vega-Peñaloza、Mattia Silvi、Paolo Melchiorre

  DOI：10.1021/acscatal.7b03788

  日期：2018.2.2

  The direct introduction of sp3 carbon fragments at the β position of α,β-unsaturated aldehydes is greatly complicated by competing 1,2-addition manifolds. Previous catalytic enantioselective conjugate addition methods, based on the use of organometallic reagents or ground-state iminium ion activation, could not provide general and efficient solutions. We report herein that, by turning them into strong

  通过竞争1,2-加成歧管，在α，β-不饱和醛的β位置直接引入sp 3碳片段变得非常复杂。现有的基于使用有机金属试剂或基态亚胺离子活化的催化对映选择性共轭加成方法无法提供通用且有效的解决方案。我们在这里报道，通过将它们变成强氧化剂，手性亚胺离子的可见光激发触发了立体可控的自由基途径，该途径独家提供了带有各种烷基片段的高度对映体富集的β-取代的醛。
• A Versatile New Catalyst for the Enantioselective Isomerization of Allylic Alcohols to Aldehydes:  Scope and Mechanistic Studies
  作者：Ken Tanaka、Gregory C. Fu

  DOI：10.1021/jo010792v

  日期：2001.11.1

  [Rh(cod)(2)]BF(4), serves as an effective catalyst for asymmetric isomerizations of allylic alcohols to aldehydes, furnishing improved yields, scope, and enantioselectivities relative to previously reported methods. The catalyst is air-stable and can be recovered at the end of the reaction. Mechanistic studies establish that the isomerization proceeds via an intramolecular 1,3-hydrogen migration and that

  合成了一种新的平面手性双齿磷酸二茂铁配体（2）并对其结构进行了表征。衍生的铑配合物[Rh（cod）（2）] BF（4）可作为有效的催化剂，用于烯丙基醇向醛的不对称异构化，相对于先前报道的方法，可提供更高的收率，范围和对映选择性。该催化剂是空气稳定的，并且可以在反应结束时回收。机理研究表明，异构化是通过分子内的1,3-氢迁移进行的，并且催化剂区分了对映体C1氢。
• Iridium‐Catalyzed Asymmetric Isomerization of Primary Allylic Alcohols Using MaxPHOX Ligands: Experimental and Theoretical Study
  作者：Albert Cabré、Martí Garçon、Albert Gallen、Lorenzo Grisoni、Arnald Grabulosa、Xavier Verdaguer、Antoni Riera

  DOI：10.1002/cctc.202000442

  日期：2020.8.20

  isomerization of primary allylic alcohols to chiral aldehydes using iridium‐catalysts bearing P,N‐MaxPHOX ligands has been studied. These catalysts can be fine‐tuned as they present three different stereogenic centers to modulate both the reactivity and enantioselectivity of a family of different substrates. The experimental part is supported by a DFT study of the reaction mechanism, which provides new

  研究了使用带有P，N- MaxPHOX配体的铱催化剂将伯烯丙基醇不对称异构化为手性醛。可对这些催化剂进行微调，因为它们具有三个不同的立体异构中心，可调节一系列不同底物的反应性和对映选择性。实验部分得到了反应机理的DFT研究的支持，该研究为这种转化的关键步骤提供了新的见解。
• Expanded scope for the iridium-catalyzed asymmetric isomerization of primary allylic alcohols using readily accessible second-generation catalysts
  作者：Luca Mantilli、Clément Mazet

  DOI：10.1039/b920342g

  日期：——

  A second generation of chiral (P,N)-iridium catalysts--readily accessible from inexpensive L-serine--displays expanded scope for the asymmetric isomerization of primary allylic alcohols.

  第二代手性（P，N）-铱催化剂-易于从廉价的L-丝氨酸中获得-显示了伯烯丙基醇不对称异构化的扩展范围。
• Iridium-Catalyzed Asymmetric Isomerization of Primary Allylic Alcohols
  作者：Luca Mantilli、David Gérard、Sonya Torche、Céline Besnard、Clément Mazet

  DOI：10.1002/anie.200901863

  日期：2009.6.29

  AbstractNothing to sm(Ir)k at: Under appropriate reaction conditions, iridium hydride catalysts promote the isomerization of primary allylic alcohols. The best catalysts, like (R)‐1 (P green, O red, N blue, Ir yellow), deliver the desired chiral aldehydes with excellent enantioselectivity and good yields. Mechanistic hypotheses have been developed on the basis of preliminary investigations.magnified image