(R)-1-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-3-oxopropyl (S)-3,3,3-trifluoro-2-methoxy-2-phenylpropanoate | 1196498-91-5

• 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: (R)-1-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-3-oxopropyl (S)-3,3,3-trifluoro-2-methoxy-2-phenylpropanoate
• CAS: 1196498-91-5
• 化学式: C₂₀H₂₅F₃O₆
• 分子量: 418.41
• InChiKey: YCLVSHKHWILJPT-VCBZYWHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.38
• 重原子数：
  29.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 4-二甲氨基吡啶 、 D-组氨酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 10.0h， 生成 (R)-1-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-3-oxopropyl (S)-3,3,3-trifluoro-2-methoxy-2-phenylpropanoate
  参考文献：
  名称：

  组氨酸催化的不对称醛的不对称醛醇加成反应：对其机理的认识

  摘要：

  描述了可烯化醛之间不对称交叉羟醛加成的广泛研究，并为组氨酸催化的羟醛加成提供了更深入的了解。特别是，讨论了这些反应的对映选择性和非对映选择性。通过使用不同的过渡状态模型来解释配置结果的规则和预测。这些讨论已通过大量的计算得到证实。

  DOI：

  10.1021/jo202558f

文献信息

• Transition-metal-free stereoselective synthesis of C(1)–C(6) fragment of epothilones and their structural analogues
  作者：Denis G. Shklyaruck、Artsiom N. Fedarkevich、Yurii Yu. Kozyrkov

  DOI：10.1016/j.tet.2016.10.038

  日期：2016.12

  Two efficient and scalable asymmetric syntheses of C(1)–C(6) fragment of epothilones and their structural analogues from commercially available 1,2:5,6-di-O-isopropylidene-d-mannitol have been performed in seven and 12 steps with 35% and 36% overall yields, respectively. Both the approaches include of one-pot, sequential transformations. The key steps are l-histidine-catalyzed aldol reaction, Barton–McCombie

  从商购的1,2- C（1）-C（6）埃坡霉素的片段和它们的结构类似物中的两个有效和可伸缩不对称合成：5,6-二- ö异亚丙基d -mannitol在七个和12已经进行了分别获得35％和36％的总收益。两种方法都包括一锅法，顺序变换。关键步骤是l-组氨酸催化的羟醛反应，Barton-McCombie脱氧，锌介导的Vasella片段化和氧化腈合成。
• Stereoselectivities of Histidine-Catalyzed Asymmetric Aldol Additions and Contrasts with Proline Catalysis: A Quantum Mechanical Analysis
  作者：Yu-hong Lam、K. N. Houk、Ulf Scheffler、Rainer Mahrwald

  DOI：10.1021/ja2118392

  日期：2012.4.11

  Quantum mechanical calculations reveal the origin of diastereo- and enantioselectivities of aldol reactions between aldehydes catalyzed by histidine, and differences between related reactions catalyzed by proline. A stereochemical model that explains both the sense and the high levels of the experimentally observed stereoselectivity is proposed. The computations suggest that both the imidazolium and the carboxylic acid functionalities of histidine are viable hydrogen-bond donors that can stabilize the cyclic aldolization transition state. The stereoselectivity is proposed to arise from minimization of gauche interactions around the forming C-C bond.
• Isoleucine-Catalyzed Direct Asymmetric Aldol Addition of Enolizable Aldehydes
  作者：Kerstin Rohr、Rainer Mahrwald

  DOI：10.1021/ol300754n

  日期：2012.4.20

  Isoleucine-catalyzed direct enantioselective aldol additions between enolizable aldehydes are reported. Intermediate acetal structures dictate the configurative outcome and were supported by a hydrogen bond. This direct isoleucine-catalyzed aldol addition represents a welcome complement to both proline- and histidine-catalyzed aldol additions of enolizable aldehydes.