ethyl 5-(diethoxyphosphoryl)-5-nitropentanoate | 1445598-05-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 5-(diethoxyphosphoryl)-5-nitropentanoate
• 英文别名: Ethyl 5-diethoxyphosphoryl-5-nitropentanoate；ethyl 5-diethoxyphosphoryl-5-nitropentanoate
• CAS: 1445598-05-9
• 化学式: C₁₁H₂₂NO₇P
• 分子量: 311.272
• InChiKey: ORLJWGTZFNZAGV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  20
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-(3-bromophenyl)prop-2-en-1-one 、 ethyl 5-(diethoxyphosphoryl)-5-nitropentanoate 在 3-((3,5-bis(trifluoromethyl)phenyl)amino)-4-(((S)-((1S,2S,4S,5R)-5-ethylquinuclidin-2-yl)(6-methoxyquinolin-4-yl)methyl)amino)cyclobut-3-ene-1,2-dione 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 、 均三甲苯 为溶剂， 反应 22.0h， 以95%的产率得到ethyl (R)-8-(3-bromophenyl)-5-(diethoxyphosphoryl)-5-nitro-8-oxooctanoate
  参考文献：
  名称：

  Quinine-Derived Thiourea and Squaramide Catalyzed Conjugate Addition of α-Nitrophosphonates to Enones: Asymmetric Synthesis of Quaternary α-Aminophosphonates

  摘要：

  Conjugate addition of a-nitrophosphonates to enones was carried out in the presence of two sets of organocatalysts, viz. a quinine-thiourea and a quinine-squaramide. The quinine-thiourea provided the products possessing an a-quaternary chiral center in high enantioselectivities only in the case of electron rich enones. On the other hand, the quinine-squaramide was more efficient in that a wide variety of electron rich and electron poor enones underwent Michael addition of nitrophosphonates to afford the quaternary a-nitrophosphonates in excellent yields and enantioselectivities. The hydrogen bonding donor ability of the bifunctional catalyst, as shown in the proposed transition states, appears primarily responsible for the observed selectivity. However, a favorable p-stacking between the aryl groups of thiourea/squaramide and aryl vinyl ketone also appeared favorable. The reaction was amenable to scale up, and the enantioenriched quaternary a-nitrophosphonates could be easily transformed to synthetically and biologically useful quaternary a-aminophosphonates and other multifunctional molecules.

  DOI：

  10.1021/jo502332r
• 作为产物：
  描述：

  戊二酸单乙酯酰氯 在 吡啶 、 盐酸羟胺 、 间氯过氧苯甲酸 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 84.0h， 生成 ethyl 5-(diethoxyphosphoryl)-5-nitropentanoate
  参考文献：
  名称：

  四取代手性α-碳的奎宁-方胺催化硝基膦酸酯与乙烯基砜的迈克尔加成反应，对映体选择性合成α-氨基-γ-磺酰基膦酸酯

  摘要：

  具有关键的四取代手性α-碳中心的α-硝基-γ-磺酰基膦酸酯是通过奎宁-方酰胺催化的α-硝基膦酸酯向芳基乙烯基砜的共轭加成反应首次以高收率和对映选择性合成的。这里介绍的有关将硝基磺酰基膦酸酯转化为氨基磺酰基膦酸酯，在磺酰基基团的α位进行烷基化，然后进行脱磺化和扩大共轭物添加量的典型实例突出了该方法的实际应用。

  DOI：

  10.1002/adsc.201300224

文献信息

• Quinine-Derived Thiourea and Squaramide Catalyzed Conjugate Addition of α-Nitrophosphonates to Enones: Asymmetric Synthesis of Quaternary α-Aminophosphonates
  作者：Kalisankar Bera、Irishi N. N. Namboothiri

  DOI：10.1021/jo502332r

  日期：2015.2.6

  Conjugate addition of a-nitrophosphonates to enones was carried out in the presence of two sets of organocatalysts, viz. a quinine-thiourea and a quinine-squaramide. The quinine-thiourea provided the products possessing an a-quaternary chiral center in high enantioselectivities only in the case of electron rich enones. On the other hand, the quinine-squaramide was more efficient in that a wide variety of electron rich and electron poor enones underwent Michael addition of nitrophosphonates to afford the quaternary a-nitrophosphonates in excellent yields and enantioselectivities. The hydrogen bonding donor ability of the bifunctional catalyst, as shown in the proposed transition states, appears primarily responsible for the observed selectivity. However, a favorable p-stacking between the aryl groups of thiourea/squaramide and aryl vinyl ketone also appeared favorable. The reaction was amenable to scale up, and the enantioenriched quaternary a-nitrophosphonates could be easily transformed to synthetically and biologically useful quaternary a-aminophosphonates and other multifunctional molecules.
• Enantioselective Synthesis of α-Amino-γ-sulfonyl Phosphonates with a Tetrasubstituted Chiral α-Carbon<i>via</i>Quinine-Squaramide-Catalyzed Michael Addition of Nitrophosphonates to Vinyl Sulfones
  作者：Kalisankar Bera、Irishi N. N. Namboothiri

  DOI：10.1002/adsc.201300224

  日期：2013.5.3

  α‐Nitro‐γ‐sulfonyl phosphonates with a key tetrasubstituted chiral α‐carbon center have been synthesized for the first time in high yield and enantioselectivity through a quinine‐squaramide‐catalyzed conjugate addition of α‐nitro phosphonates to aryl vinyl sulfones. Representative examples presented here for the transformation of nitrosulfonyl phosphonates to aminosulfonyl phosphonates, alkylation

  具有关键的四取代手性α-碳中心的α-硝基-γ-磺酰基膦酸酯是通过奎宁-方酰胺催化的α-硝基膦酸酯向芳基乙烯基砜的共轭加成反应首次以高收率和对映选择性合成的。这里介绍的有关将硝基磺酰基膦酸酯转化为氨基磺酰基膦酸酯，在磺酰基基团的α位进行烷基化，然后进行脱磺化和扩大共轭物添加量的典型实例突出了该方法的实际应用。