(R)-3-hydroxy-4,4-dimethoxy-2,2-dimethylbutyraldehyde | 1196498-59-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-3-hydroxy-4,4-dimethoxy-2,2-dimethylbutyraldehyde
• 英文别名: (R)-3-hydroxy-4,4-dimethoxy-2,2-dimethylbutanal；(3R)-3-hydroxy-4,4-dimethoxy-2,2-dimethylbutanal
• CAS: 1196498-59-5
• 化学式: C₈H₁₆O₄
• 分子量: 176.213
• InChiKey: QRCQULBURGWQDD-LURJTMIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-3-hydroxy-4,4-dimethoxy-2,2-dimethylbutyraldehyde 、 (R)-(+)-α-甲氧基-α-(三氟甲基)苯乙酸 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 生成
  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
• 作为产物：
  描述：

  乙二醛-1,1-二甲基乙缩醛溶液 、 异丁醛 在 L-组氨酸 作用下， 以 水 为溶剂， 反应 20.0h， 生成 (S)-3-hydroxy-4,4-dimethoxy-2,2-dimethylbutyraldehyde 、 (R)-3-hydroxy-4,4-dimethoxy-2,2-dimethylbutyraldehyde
  参考文献：
  名称：

  Stereoselectivities of Histidine-Catalyzed Asymmetric Aldol Additions and Contrasts with Proline Catalysis: A Quantum Mechanical Analysis

  摘要：

  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.

  DOI：

  10.1021/ja2118392

文献信息

• Asymmetric Histidine-Catalyzed Cross-Aldol Reactions of Enolizable Aldehydes: Access to Defined Configured Quaternary Stereogenic Centers
  作者：Morris Markert、Ulf Scheffler、Rainer Mahrwald

  DOI：10.1021/ja907054y

  日期：2009.11.25

  A histidine-catalyzed asymmetric direct cross-aldol reaction of enolizable aldehydes is described. In contrast to proline, histidine is able to clearly differentiate the reactivity of various aldehydes. In addition, this approach provides access to syn-configured B-hydroxyaldehydes. Thus, by application of this new methodology, defined-configuration quaternary stereocenters can be constructed with ease. The utility of this method is demonstrated in several total syntheses of branched-chain carbohydrates.
• Histidine-Catalyzed Asymmetric Aldol Addition of Enolizable Aldehydes: Insights into its Mechanism
  作者：Ulf Scheffler、Rainer Mahrwald

  DOI：10.1021/jo202558f

  日期：2012.3.2

  Extensive studies of asymmetric cross-aldol addition between enolizable aldehydes are described and provide a deeper insight into histidine-catalyzed aldol additions. In particular, aspects of enantio- as well as diastereoselectivity of these reactions are discussed. Rules and predictions of configurative outcome are explained by using different transition-state models. These discussions are confirmed

  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。
• 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.