2-(1,3-benzodioxol-5-yl)ethyl 2-diazo-2-(diethoxyphosphoryl)acetate | 1607455-09-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 2-(1,3-benzodioxol-5-yl)ethyl 2-diazo-2-(diethoxyphosphoryl)acetate
• 英文别名: 2-(1,3-Benzodioxol-5-yl)ethyl 2-diazo-2-[diethoxy(oxido)phosphaniumyl]acetate；2-(1,3-benzodioxol-5-yl)ethyl 2-diazo-2-[diethoxy(oxido)phosphaniumyl]acetate
• CAS: 1607455-09-3
• 化学式: C₁₅H₁₉N₂O₇P
• 分子量: 370.299
• InChiKey: UVXAVRDVIZKXHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  25
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  88.3
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-(1,3-benzodioxol-5-yl)ethyl 2-diazo-2-(diethoxyphosphoryl)acetate 在 辛酸铑 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 23.25h， 生成 4-(1,3-benzodioxol-5-yl)-3-methylidenedihydrofuran-2(3H)-one
  参考文献：
  名称：

  A One-Pot C–H Insertion/Olefination Sequence for the Formation of α-Alkylidene-γ-butyrolactones

  摘要：

  A one-pot C-H insertion/olefination sequence for the conversion of alpha-diazo-alpha-(dialkoxyphosphoryl)acetates into alpha-alkylidene-gamma-butyrolactones is reported. The key C-H insertion process is achieved using a catalytic amount of a dirhodium carboxylate catalyst, using operationally simple conditions. The size and electronic properties of the attached substituents were found to influence the regio- and diastereoselectivity of the process. The utility of the process is demonstrated by the synthesis of a known Staphylococcus aureus (MRSA) virulence inhibitor.

  DOI：

  10.1021/ol501092m
• 作为产物：
  描述：

  2-(1,3-benzodioxol-5-yl)ethyl 2-(diethoxyphosphoryl)acetate 在 lithium hexamethyldisilazane 、 4-乙酰氨基苯磺酰叠氮 作用下， 以 四氢呋喃 为溶剂， 反应 1.17h， 以55%的产率得到2-(1,3-benzodioxol-5-yl)ethyl 2-diazo-2-(diethoxyphosphoryl)acetate
  参考文献：
  名称：

  A One-Pot C–H Insertion/Olefination Sequence for the Formation of α-Alkylidene-γ-butyrolactones

  摘要：

  A one-pot C-H insertion/olefination sequence for the conversion of alpha-diazo-alpha-(dialkoxyphosphoryl)acetates into alpha-alkylidene-gamma-butyrolactones is reported. The key C-H insertion process is achieved using a catalytic amount of a dirhodium carboxylate catalyst, using operationally simple conditions. The size and electronic properties of the attached substituents were found to influence the regio- and diastereoselectivity of the process. The utility of the process is demonstrated by the synthesis of a known Staphylococcus aureus (MRSA) virulence inhibitor.

  DOI：

  10.1021/ol501092m

文献信息

• Phosphorylated cyclopropanes in the synthesis of α-alkylidene-γ-butyrolactones: total synthesis of (±)-savinin, (±)-gadain and (±)-peperomin E
  作者：Matthew G. Lloyd、Richard J. K. Taylor、William P. Unsworth

  DOI：10.1039/c6ob01527a

  日期：——

  Phosphorylated cyclopropanes, generated via the Rh(II)-catalysed intramolecular cyclopropanation of α-(diethoxyphosphoryl)acetates, have been found to be useful precursors in the synthesis of α-alkylidene-γ-butyrolactones. These cyclopropyl intermediates undergo regioselective reductive ring-opening and subsequent Horner–Wadsworth–Emmons olefination to complete the synthesis. Total syntheses of (±)-savinin

  已经发现，通过Rh（II）催化的α-（二乙氧基磷酰基）乙酸酯的分子内环丙烷化生成的磷酸化环丙烷是α-亚烷基-γ-丁内酯合成中的有用前体。这些环丙基中间体会进行区域选择性还原性开环反应，随后进行Horner-Wadsworth-Emmons烯化反应以完成合成。（±）-savinin和（±）-gadain的总合成，以及（±）-peperomin E的第一个总合成，均使用此方法进行了描述。
• A One-Pot C–H Insertion/Olefination Sequence for the Formation of α-Alkylidene-γ-butyrolactones
  作者：Matthew G. Lloyd、Richard J. K. Taylor、William P. Unsworth

  DOI：10.1021/ol501092m

  日期：2014.5.16

  A one-pot C-H insertion/olefination sequence for the conversion of alpha-diazo-alpha-(dialkoxyphosphoryl)acetates into alpha-alkylidene-gamma-butyrolactones is reported. The key C-H insertion process is achieved using a catalytic amount of a dirhodium carboxylate catalyst, using operationally simple conditions. The size and electronic properties of the attached substituents were found to influence the regio- and diastereoselectivity of the process. The utility of the process is demonstrated by the synthesis of a known Staphylococcus aureus (MRSA) virulence inhibitor.
• α-Alkylidene-γ-butyrolactone synthesis via one-pot C–H insertion/olefination: substrate scope and the total synthesis of (±)-cedarmycins A and B
  作者：Matthew G. Lloyd、Mariantonietta D'Acunto、Richard J.K. Taylor、William P. Unsworth

  DOI：10.1016/j.tet.2014.09.054

  日期：2015.9

  A system for the synthesis of alpha-alkylidene-gamma-butyrolactones via a one-pot C-H insertion/olefination sequence is described. The process is based on the rhodium catalysed C-H insertion reaction of alpha-diazoa-(diethoxyphosphoryl)acetates. The mild reaction conditions, operational simplicity and ready availability of starting materials are all key features. A wide range of successful reaction systems are reported (41 examples) highlighting the generality of the method. The application of this method in the total synthesis of the natural products (+/-)-cedarmycins A and B is also described. (C) 2014 Elsevier Ltd. All rights reserved.