(R)-3-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-3-hydroxy-2,2-dimethylpropanal | 1196498-56-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-3-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-3-hydroxy-2,2-dimethylpropanal
• 英文别名: (3R,4R)-3-[2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-2,2-dimethylpropionaldehyde；3,4-(R,R)-3-[2,2-dimethyl-(1,3)dioxolan-4-yl]-3-hydroxy-2,2-dimethyl-propionaldehyde；(3R)-3-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-2,2-dimethylpropanal
• CAS: 1196498-56-2
• 化学式: C₁₀H₁₈O₄
• 分子量: 202.251
• InChiKey: KIVTUGFUKDXZMR-SFYZADRCSA-N

物化性质

• 沸点：
  286.2±25.0 °C(Predicted)
• 密度：
  1.068±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 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-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-3-hydroxy-2,2-dimethylpropanal 在 咪唑 、 盐酸 、 lithium aluminium tetrahydride 、 偶氮二异丁腈 、 四丁基氟化铵 、 氨 、 碘 、 三正丁基氢锡 、 4-甲基苯磺酸吡啶 、 sodium hydride 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 水 、 甲苯 、 乙腈 、 mineral oil 、 正戊烷 为溶剂， 反应 82.67h， 生成 (4S)-4-(2-methyl-3-oxohept-6-en-2-yl)-2,2-dimethyl[1,3]dioxane
  参考文献：
  名称：

  埃坡霉素的C（1）–C（6）片段及其结构类似物的无过渡金属立体选择性合成

  摘要：

  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。

  DOI：

  10.1016/j.tet.2016.10.038
• 作为产物：
  描述：

  双丙酮-D-甘露糖醇 在 sodium periodate 、 L-组氨酸 作用下， 以 aq. phosphate buffer 、 二氯甲烷 、 水 为溶剂， 反应 12.08h， 生成 (R)-3-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-3-hydroxy-2,2-dimethylpropanal
  参考文献：
  名称：

  埃坡霉素的C（1）–C（6）片段及其结构类似物的无过渡金属立体选择性合成

  摘要：

  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。

  DOI：

  10.1016/j.tet.2016.10.038

文献信息

• 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。
• 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.
• 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.
• 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。