diethyl (3,3,3-trifluoro-2-oxopropyl)phosphonate | 85234-36-2

• 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: diethyl (3,3,3-trifluoro-2-oxopropyl)phosphonate
• 英文别名: diethyl 3,3,3-trifluoro-2-oxopropylphosphonate；(3,3,3-trifluoropropyl-2-oxo)phosphonate；3-diethoxyphosphoryl-1,1,1-trifluoropropan-2-one
• CAS: 85234-36-2
• 化学式: C₇H₁₂F₃O₄P
• 分子量: 248.139
• InChiKey: LTUZKKYWACXAOK-UHFFFAOYSA-N

物化性质

• 沸点：
  58-60 °C(Press: 0.1 Torr)
• 密度：
  1.276±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  diethyl (3,3,3-trifluoro-2-oxopropyl)phosphonate 在 4-二甲氨基吡啶 、 Candida antarctica lipase B 、 N,N'-二环己基碳二亚胺 作用下， 以 正丁醇 、 苯 为溶剂， 反应 40.0h， 生成 (R)-diethyl 3,3,3-trifluoro-2-hydroxypropanephosphonate
  参考文献：
  名称：

  Enzymatic synthesis of optically active trifluoromethylated 1- and 2-hydroxyalkanephosphonates

  摘要：

  Convenient enzymatic methods have been developed for the preparation of chiral 1- and 2-hydroxyalkanephosphonates bearing a trifluoromethyl moiety with high enantiomeric excess via Candida antarctica lipase B-, Mucor miehei lipase-catalyzed alcoholysis and C. rugosa lipase-catalyzed hydrolysis in organic media. The enantiomeric excess of such trifluoromethylated carbinols was determined using quinine as a chiral solvating agent. The catalytic preference was assigned according to the Kusumi-Ohtani method. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)01559-4
• 作为产物：
  描述：

  diethyl (3,3,3-trifluoro-2,2-dihydroxypropyl)phosphonate 生成 diethyl (3,3,3-trifluoro-2-oxopropyl)phosphonate
  参考文献：
  名称：

  The stereospecific synthesis of (Z)- and (E)-diethyl (3,3,3-trifluoro-1-propenyl)phosphonate

  摘要：

  DOI：

  10.1021/jo00251a044

文献信息

• Synthesis of Fluoroalkylated β-Aminophosphonates and Pyridines from Primary β-Enaminophosphonates
  作者：Francisco Palacios、Ana M. Ochoa de Retana、Julen Oyarzabal、Sergio Pascual、Guillermo Fernández de Trocóniz

  DOI：10.1021/jo8005667

  日期：2008.6.1

  and efficient stereoselective synthesis of fluorine containing β-aminophosphonates by reduction of β-enaminophosphonates is described. Reduction with sodium cyanborohydride in the presence of zinc chloride and the catalytic hydrogenation of β-enaminophosphonates gives β-aminophosphonates. β-Enaminophosphonates are also used as intermediates for the regioselective synthesis of fluoroalkyl-substituted pyridines

  描述了通过还原β-烯氨基膦酸酯来简单且有效的立体选择性地合成含氟的β-氨基膦酸酯的方法。在氯化锌存在下用氰基硼氢化钠还原，然后β-烯氨基膦酸酯催化加氢，得到β-氨基膦酸酯。β-烯氨基膦酸酯也用作氟烷基取代的吡啶的区域选择性合成的中间体。
• An effective synthetic route to ortho-difluoromethyl arylphosphosphonates: studies on the reactivity of phosphorus- and fluorine-containing functions
  作者：Sergey N. Tverdomed、Jacek Kolanowski、Enno Lork、Gerd-Volker Röschenthaler

  DOI：10.1016/j.tet.2011.03.076

  日期：2011.5

  Herein, we report a new and convenient methodology for the synthesis of ortho-XCF2 arylphosphonates via Diels–Alder reaction of selected 1,3-butadienes with XCF2–≡–P(O)(OEt)2, followed by the aromatization of the cyclic vinylphosphonates obtained using the KMnO4/Al2O3 system. The reactivity of ortho-XCF2 arylphosphonates was then examined to give the respective dichlorides that were converted to the

  本文中，我们报告了一种新的便捷方法，用于通过所选1,3-丁二烯与XCF 2 – 2 –P（O）（OEt）2的Diels–Alder反应合成邻-XCF 2芳基膦酸酯，然后进行芳构化。使用KMnO 4 / Al 2 O 3系统获得的环状乙烯基膦酸酯。然后检查邻-XCF 2芳基膦酸酯的反应性，得到各自的二氯化物，将其转化为相应的膦酸，氧化膦或羧酸（在CF 2 Br基团水解时）。当邻位-XCF 2用Zn / CuBr和亲电子试剂处理芳基膦酸酯（X = Br），仅分离出二聚体产物ArCF CFAr。然而，CF 2 H基团的锂化（X ＝ H）允许获得被各种亲电试剂亲核取代的产物。
• Regioselective Synthesis of Fluoroalkylated β-Aminophosphorus Derivatives and Aziridines from Phosphorylated Oximes and Nucleophilic Reagents
  作者：Francisco Palacios、Ana M. Ochoa de Retana、José M. Alonso

  DOI：10.1021/jo060865g

  日期：2006.8.1

  Grignard reagents to functionalized ketoxime-phosphine oxides and -phosphonates is described. Aziridines are used as intermediates for the regioselective synthesis of fluorine containing β-amino phosphine oxides and β-amino phosphonates. Amino phosphorus derivatives can also be obtained from ketoximes derived from phosphine oxides and phosphonates with sodium borohydride.

  描述了通过非对映选择性地将甲醇盐，咪唑，苯硫醇和格氏试剂非对映选择性加成到官能化的酮肟-膦氧化物和-膦酸酯上的简单有效的立体选择性合成氟烷基取代的氮丙啶-2-膦氧化物和-膦酸酯的方法。氮丙啶被用作区域选择性合成含氟的β-氨基膦氧化物和β-氨基膦酸酯的中间体。氨基磷衍生物也可以从衍生自氧化膦和膦酸酯与硼氢化钠的酮肟中获得。
• Convenient and Efficient Access to Fluoroalkylated Vinylphosphonates via Highly Regio- and Stereoselective Hydrometalation or Carbometalation Reactions of Fluorine-Containing Alkynylphosphonates
  作者：Tsutomu Konno、Atsunori Morigaki、Kazuo Ninomiya、Tomotsugu Miyabe、Takashi Ishihara

  DOI：10.1055/s-2008-1032143

  日期：2008.2

  The hydrostannation, carbocupration, and carbozincation reactions of fluorinated alkynylphosphonates were investigated. The hydrostannation reaction proceeded smoothly without an additive (e.g., BEt3/O2, AIBN) to give the corresponding vinylstannanes in a highly regio- and stereoselective manner. Various cuprates, prepared from organolithium, Grignard, and organozinc reagents, could participate nicely in the carbocupration reactions, the corresponding adducts were obtained in good to high yields. Dialkylzinc reagents reacted smoothly with the alkynylphosphonates even in the absence of copper salt to afford the corresponding adducts in good yields.

  对氟化烷炔磷酸酯的氢锡化、碳铜化和碳锌化反应进行了研究。氢锡化反应在没有添加剂（如 BEt3/O2, AIBN）的情况下顺利进行，以高度区域选择性和立体选择性生成相应的乙烯基锡化物。多种铜盐，从有机锂、格林尼亚试剂和有机锌试剂制备的，可以很好地参与碳铜化反应，相应的加成产物以良好至高的产率获得。双烷基锌试剂即使在没有铜盐的情况下也能与烷炔磷酸酯顺利反应，获得相应的加成产物，产率良好。
• Steric Enforcement of <i>cis</i>-Epoxide Formation in the Radical C–O-Coupling Reaction by Which (<i>S</i>)-2-Hydroxypropylphosphonate Epoxidase (HppE) Produces Fosfomycin
  作者：Shengbin Zhou、Juan Pan、Katherine M. Davis、Irene Schaperdoth、Bo Wang、Amie K. Boal、Carsten Krebs、J. Martin Bollinger

  DOI：10.1021/jacs.9b10974

  日期：2019.12.26

  residues - Leu120, Leu144, Phe182, and Leu193 - close to C3 in one of the complexes. Replacement of Leu193 in the substrate C3 pocket with the bulkier Phe enhances stereoselectivity (cis:trans ~ 99:1), whereas the Leu120Phe substitution in the product C3 pocket diminishes it (~ 82:18). Retention of C1 configuration and trans-epoxide formation become predominant with the bulk-reducing Phe182Ala substitution

  (S)-2-羟丙基膦酸酯 [(S)-2-HPP, 1] 环氧化酶 (HppE) 在其非血红素铁辅因子处减少 H2O2，以安装抗生素磷霉素的环氧乙烷“弹头”。1 的 C1 pro-R 氢被其 C2 氧净置换，在 C1 处发生构型反转，产生药物的顺式环氧化物 [(1R,2S)-环氧丙基膦酸 (cis-Fos, 2)]。在这里，我们表明 HppE 通过自由基偶联机制的空间引导实现了约 95% 的 C1 反转和顺式环氧化物形成的选择性。HppE•FeII•1 和 HppE•ZnII•2 复合物的已发表结构揭示了底物和产物 C3 的不同口袋，并确定了四种疏水性残基 - Leu120、Leu144、Phe182 和 Leu193 - 在其中一个复合物中接近 C3。用体积更大的 Phe 替换底物 C3 口袋中的 Leu193 增强了立体选择性（顺式：反式~99:1），而产物 C3 口袋中的 Leu120Phe