(+)-(R)-3,3,5-trimethyl-5-(nitromethyl)cyclohexan-1-one | 1312208-26-6

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: (+)-(R)-3,3,5-trimethyl-5-(nitromethyl)cyclohexan-1-one
• 英文别名: (R)-3,3,5-trimethyl-5-(nitromethyl)cyclohexanone；(5R)-3,3,5-trimethyl-5-(nitromethyl)cyclohexan-1-one
• CAS: 1312208-26-6
• 化学式: C₁₀H₁₇NO₃
• 分子量: 199.25
• InChiKey: VNHSGIMBBBITOC-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  异佛尔酮 、 硝基甲烷 在 苯甲酸 、 9-氨基-(9-脱氧)表辛可宁三盐酸盐 作用下， 以 甲苯 为溶剂， 20.0~25.0 ℃ 、1000.01 MPa 条件下， 反应 20.0h， 以74%的产率得到(+)-(R)-3,3,5-trimethyl-5-(nitromethyl)cyclohexan-1-one
  参考文献：
  名称：

  Effect of High Pressure on the Organocatalytic Asymmetric Michael Reaction: Highly Enantioselective Synthesis of γ-Nitroketones with Quaternary Stereogenic Centers

  摘要：

  The significant effect of hydrostatic pressure on the difficult organocatalytic 1,4-conjugate addition of nitroalkanes to prochiral sterically congested beta,beta-disubstituted enones is demonstrated. This approach allows for the synthesis of gamma-nitroketones containing quaternary stereogenic centers with good yields, excellent enantioselectivity, and low loading (1-5 mol %) of simple chiral primary amine catalysts.

  DOI：

  10.1021/ol201275h

文献信息

• A versatile approach to functionalized cyclic ketones bearing quaternary carbon stereocenters via organocatalytic asymmetric conjugate addition of nitroalkanes to cyclic β-substituted α,β-Enones
  作者：Si-Jia Yu、Ya-Nan Zhu、Jian-Liang Ye、Pei-Qiang Huang

  DOI：10.1016/j.tet.2021.132005

  日期：2021.3

  quaternary stereogenic centers at β-C has been developed. This is an extension of the method that we developed during the total synthesis of (−)-haliclonin A, which features the employment of structurally relatively simple, cheap and easily available primary amine-thiourea derived from (R,R)-1,2-diaminocyclohexane as the chiral catalyst. The method shows wide substrate scope, good functional group tolerance

  已经开发了一种通用的有机催化不对称共轭硝基链烷烃加成到β-取代的环状α，β-烯酮上的环状酮，其在β-C处带有全碳四元立体异构中心。这是我们在（-）-haliclonin A的全合成过程中开发的方法的扩展，该方法的特点是采用结构相对简单，廉价且易于获得的伯胺-硫脲衍生自（R，R）-1,2-二氨基环己烷为手性催化剂。该方法显示了广泛的底物范围，良好的官能团耐受性，可快速获得多功能手性化合物。该方法的合成潜力通过将硝基酮加合物一步转化为其他四类化合物来证明。通过将手性HPLC分析的保留时间和比旋光度与已知化合物的保留时间进行比较，可以确定加合物的绝对构型。根据DFT计算研究，合理选择了对映选择性控制机制。
• Effect of High Pressure on the Organocatalytic Asymmetric Michael Reaction: Highly Enantioselective Synthesis of γ-Nitroketones with Quaternary Stereogenic Centers
  作者：Piotr Kwiatkowski、Krzysztof Dudziński、Dawid Łyżwa

  DOI：10.1021/ol201275h

  日期：2011.7.15

  The significant effect of hydrostatic pressure on the difficult organocatalytic 1,4-conjugate addition of nitroalkanes to prochiral sterically congested beta,beta-disubstituted enones is demonstrated. This approach allows for the synthesis of gamma-nitroketones containing quaternary stereogenic centers with good yields, excellent enantioselectivity, and low loading (1-5 mol %) of simple chiral primary amine catalysts.