2,2-diethoxypent-4-enal | 676557-38-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-diethoxypent-4-enal
• CAS: 676557-38-3
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: JHZVTAGJOTWQMS-UHFFFAOYSA-N

物化性质

• 沸点：
  194.2±40.0 °C(Predicted)
• 密度：
  0.944±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(triethylsilyl)-3-butyn-2-one 、 2,2-diethoxypent-4-enal 在 4 A molecular sieve 、 diethylzinc 、 (S,S)-(+)-2,6-双[2-(羟基二苯甲基)-1-吡咯烷基-甲基]-4-甲基苯酚 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 以75%的产率得到6,6-diethoxy-(5R)-hydroxy-1-triethylsilanylnon-8-en-1-yn-3-one
  参考文献：
  名称：

  Direct Catalytic Asymmetric Aldol Additions of Methyl Ynones. Spontaneous Reversal in the Sense of Enantioinduction

  摘要：

  In this Communication, we report the direct, catalytic, asymmetric aldol addition of methyl ynones using our dinuclear zinc catalyst. A spontaneous reversal in the sense of enantioinduction was observed for these reactions; formation of the (S)-enantiomer is favored in the early stages (69% ee after 5 min), whereas the (R)-enantiomer is isolated as the major product after prolonged reaction times (97% ee after 22 h). It could be shown that this reversal in enantioselectivity is due to formation of a new catalytic species which incorporates the aldol product.

  DOI：

  10.1021/ja038666r
• 作为产物：
  描述：

  2,2-二乙氧基乙酸乙酯 在 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.08h， 生成 2,2-diethoxypent-4-enal
  参考文献：
  名称：

  Direct Catalytic Asymmetric Aldol Additions of Methyl Ynones. Spontaneous Reversal in the Sense of Enantioinduction

  摘要：

  In this Communication, we report the direct, catalytic, asymmetric aldol addition of methyl ynones using our dinuclear zinc catalyst. A spontaneous reversal in the sense of enantioinduction was observed for these reactions; formation of the (S)-enantiomer is favored in the early stages (69% ee after 5 min), whereas the (R)-enantiomer is isolated as the major product after prolonged reaction times (97% ee after 22 h). It could be shown that this reversal in enantioselectivity is due to formation of a new catalytic species which incorporates the aldol product.

  DOI：

  10.1021/ja038666r

文献信息

• Total Synthesis and Stereochemical Assignment of (−)-Ushikulide A
  作者：Barry M. Trost、Brendan M. O’Boyle、Daniel Hund

  DOI：10.1021/ja906056v

  日期：2009.10.21

  We report the determination of the full stereostructure of (-)-ushikulide A (1), a spiroketal containing macrolide by total synthesis. Ushikulide A (1) was isolated from a culture broth of Streptomyces sp. IUK-102 and exhibits potent immunosuppressant activity (IC(50) = 70 nM). To embark upon an ushikulide A synthesis, a tentative assignment was made based on analogy to cytovaricin (2), a related macrolide

  我们报告了 (-)-ushikulide A (1) 的完整立体结构的测定，这是一种通过全合成含有大环内酯的螺旋缩酮。Ushikulide A (1) 是从 Streptomyces sp. 的培养液中分离出来的。IUK-102 并表现出有效的免疫抑制活性 (IC(50) = 70 nM)。为了着手进行 ushikulide A 合成，基于与 cytovaricin (2) 的类比进行了初步分配，这是一种从 Streptomyces diastatochromogenes 培养物中分离出来的相关大环内酯，其完整结构以前是通过合成和 X 射线晶体学确定的。这份报告描述了几个关键步骤的研究，即由双核锌 ProPhenol 络合物催化的直接醛醇反应，金属催化的 spiroketalization，以及应用前所未有的简单饱和醛与丙炔酸甲酯的不对称炔化反应来制备用于 Marshall-Tamaru 炔丙基化的亲核伙伴。这些研究最终实现了
• Development of ProPhenol Ligands for the Diastereo- and Enantioselective Synthesis of β-Hydroxy-α-amino Esters
  作者：Barry M. Trost、Frédéric Miege

  DOI：10.1021/ja4129394

  日期：2014.2.26

  aldol reaction between glycine Schiff bases and aldehydes is reported. The design and synthesis of new ProPhenol ligands bearing 2,5-trans-disubstituted pyrrolidines was essential for the success of this process. The transformation operates at room temperature and affords syn β-hydroxy-α-amino esters in high yields with good to excellent levels of diastereo- and enantioselectivity.

  据报道，锌-苯酚催化甘氨酸席夫碱和醛之间的直接不对称醛醇反应。带有 2,5-反式二取代吡咯烷的新 ProPhenol 配体的设计和合成对于该过程的成功至关重要。该转化在室温下进行，并以高产率提供顺式 β-羟基-α-氨基酯，并具有良好至极好的非对映选择性和对映选择性。
• Dinuclear Zinc–ProPhenol-Catalyzed Enantioselective α-Hydroxyacetate Aldol Reaction with Activated Ester Equivalents
  作者：Barry M. Trost、David J. Michaelis、Mihai I. Truica

  DOI：10.1021/ol402081p

  日期：2013.9.6

  An enantioselective alpha-hydroxyacetate aldol reaction that employs N-acetyl pyrroles as activated ester equivalents and generates syn 1,2-diols in good yield and diastereoselectivity is reported. This dinuclear zinc-ProPhenol-catalyzed transformation proceeds with high enantioselectivity with a wide variety of substrates including aryl, alyl, and alkenyl aldehydes. The resulting alpha,beta-dihydroxy activated esters are versatile intermediates for the synthesis of a variety of carboxylic acid derivatives including amides, esters, and unsymmetrical ketones.