isobutyl α-(diethoxyphosphoryl)acetate | 75412-64-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: isobutyl α-(diethoxyphosphoryl)acetate
• 英文别名: diethyl <(iso-butoxycarbonyl)methyl>phosphonate；2-methylpropyl 2-(diethoxyphosphoryl)acetate；isobutyl 2-(diethoxyphosphoryl)acetate；diethyl ((iso-butoxycarbonyl)methyl) phosphonate；Ntotxsoeyxnhmm-uhfffaoysa-；2-methylpropyl 2-diethoxyphosphorylacetate
• CAS: 75412-64-5
• 化学式: C₁₀H₂₁O₅P
• 分子量: 252.247
• InChiKey: NTOTXSOEYXNHMM-UHFFFAOYSA-N

物化性质

• 沸点：
  315.2±25.0 °C(Predicted)
• 密度：
  1.076±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  isobutyl α-(diethoxyphosphoryl)acetate 在 辛酸铑 、 4-乙酰氨基苯磺酰叠氮 、 potassium tert-butylate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 22.0h， 生成 4,4-dimethyl-3-methylenedihydrofuran-2(3H)-one
  参考文献：
  名称：

  α-Alkylidene-γ-butyrolactone synthesis via one-pot C–H insertion/olefination: substrate scope and the total synthesis of (±)-cedarmycins A and B

  摘要：

  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.

  DOI：

  10.1016/j.tet.2014.09.054
• 作为产物：
  描述：

  二乙基磷乙酸 、 异丁醇 在 1-丙基磷酸酐 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙酸乙酯 、 甲苯 为溶剂， 反应 4.0h， 以100%的产率得到isobutyl α-(diethoxyphosphoryl)acetate
  参考文献：
  名称：

  α-Alkylidene-γ-butyrolactone synthesis via one-pot C–H insertion/olefination: substrate scope and the total synthesis of (±)-cedarmycins A and B

  摘要：

  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.

  DOI：

  10.1016/j.tet.2014.09.054

文献信息

• Regio- and Stereoselective Dirhodium(II)-Catalysed Intramolecular C−H Insertion Reactions ofα-Diazo-α-(dialkoxyphosphoryl)acetamides and -acetates
  作者：Pedro M. P. Gois、Carlos A. M. Afonso

  DOI：10.1002/ejoc.200300330

  日期：2003.10

  α-Diazo-α-(dialkoxyphosphoryl)acetates and -acetamides afforded α-(dialkoxyphosphoryl)lactones and lactams, respectively, in moderate to high yields through dirhodium(II)-catalysed intramolecular carbon−hydrogen insertion reactions. In the case of α-diazo-α-(dialkoxyphosphoryl)acetamides a remarkable preference for the formation of γ-lactam was observed, with stereocontrol in favour of the trans diastereomer

  α-重氮-α-（二烷氧基磷酰基）乙酸酯和 -乙酰胺分别通过二铑（II）催化的分子内碳氢插入反应以中等至高产率提供了 α-（二烷氧基磷酰基）内酯和内酰胺。在α-重氮-α-（二烷氧基磷酰基）乙酰胺的情况下，观察到显着偏好形成γ-内酰胺，立体控制有利于反式非对映异构体。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Manganese-Catalyzed Oxophosphorylation Reaction of Carbon–Carbon Double Bonds Using Molecular Oxygen in Air
  作者：Daisuke Yamamoto、Hiromasa Ansai、Junichi Hoshino、Kazuishi Makino

  DOI：10.1248/cpb.c18-00381

  日期：2018.9.1

  A novel aerobic manganese-catalyzed oxophosphorylation reaction of carbon-carbon double bonds of styrene derivatives and vinyl ethers using diethyl H-phosphonates was developed. This direct transformation of alkenes to β-ketophosphonate readily proceeded at room temperature via the direct incorporation of molecular oxygen present in air (open flask).

  开发了一种新颖的需氧锰催化的H-膦酸二乙酯对苯乙烯衍生物和乙烯基醚的碳-碳双键进行氧代磷酸化反应。通过直接引入空气中存在的分子氧（开瓶），烯烃直接转化为β-酮膦酸酯很容易在室温下进行。
• WO2021009506A5
  申请人：——

  公开号：WO2021009506A5

  公开（公告）日：2023-07-18
• 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.

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