diethyl (1-diazo-2,2,2-trifluoroethyl)phosphonate | 906466-25-9

• 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 (1-diazo-2,2,2-trifluoroethyl)phosphonate
• 英文别名: Diethyl 1-diazo-2,2,2-trifluoroethylphosphonate；2-diazo-2-diethoxyphosphoryl-1,1,1-trifluoroethane
• CAS: 906466-25-9
• 化学式: C₆H₁₀F₃N₂O₃P
• 分子量: 246.126
• InChiKey: NYKLPZXJGCPDOZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  37.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  diethyl (1-diazo-2,2,2-trifluoroethyl)phosphonate 、 二烯丙基硫醚 在 bis(1,1,1-trifluoroacetylacetonato)copper(II) 作用下， 以 甲苯 为溶剂， 以89%的产率得到diethyl [1-(allylthio)-1-(trifluoromethyl)but-3-en-1-yl]phosphonate
  参考文献：
  名称：

  通过[2,3]-σ重排和顺序催化碳环化合成功能化的含CF 3杂环

  摘要：

  直接从重氮化合物CF 3 C（N 2）Z（Z = CO 2 Me，P（O）（OEt）2）直接开发了一种新的有效接触官能化CF 3取代的含氮或含硫的杂环的方法。该方法基于双不饱和底物的直接选择性合成，然后进行金属介导的碳环化。第一步是通过Cu（II）催化的炔丙基或/和烯丙基的硫和氮的炔丙基的[2,3]σ重排导致氟化烯炔，二烯烃，尤其是烯炔衍生物。第二步涉及通过闭环复分解和Pauson-Khand反应进行碳环化。

  DOI：

  10.1016/j.tet.2011.03.031
• 作为产物：
  描述：

  diethyl (N-benzyloxycarbonyl-2,2,2-trifluoroethaneimidoyl)phosphonate 在 sodium tetrahydroborate 、 亚硝酸异丙酯 、 palladium 10% on activated carbon 、 氢气 作用下， 以 甲醇 、 乙醚 、 氯仿 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 3.5h， 生成 diethyl (1-diazo-2,2,2-trifluoroethyl)phosphonate
  参考文献：
  名称：

  一种通过亚氨基膦酸酯合成 1-重氮-2,2,2-三氟乙基膦酸二乙酯的新制备方法

  摘要：

  开发了一种由三氟乙酸酐和氨基甲酸苄酯通过 1-苄氧基羰基亚氨基-2,2,2-三氟乙基膦酸二乙酯合成 1-重氮-2,2,2-三氟乙基膦酸二乙酯的制备方法。找到了用 SOCl2-Py 氯化 N-三氟乙酰氨基甲酸苄酯以提供亚胺酰氯、在 Arbuzov 反应条件下磷酸化后者以及用亚硝酸异丙酯重氮化氨基膦酸酯的最佳条件。

  DOI：

  10.1007/s11172-010-0051-1

文献信息

• 1-Trifluoromethyl-1-diethoxyphosphoryl Carbene: A New Synthon for the Preparation of CF₃-Containing α-Hydroxy and α-Amino Phosphonic Acid Derivatives
  作者：Sergej Osipov、Igor Titanyuk、Daria Vorob’eva、Irina Beletskaya

  DOI：10.1055/s-2006-939704

  日期：2006.6

  starting from readily available compounds. The synthetic utility of this compound is demonstrated via its Rh-catalyzed insertion into O-H and N-H bonds to produce CF 3 -substituted α-hydroxy phosphonic and α-amino phosphonic acid derivatives.

  已经从容易获得的化合物开始开发了二乙基l-重氮-2,2,2-三氟乙基膦酸酯的首次合成。该化合物的合成效用通过其 Rh 催化插入 OH 和 NH 键以产生 CF 3 -取代的 α-羟基膦酸和 α-氨基膦酸衍生物来证明。
• Trifluoromethylated cyclopropanes and epoxides from CuI-mediated transformations of α-trifluoromethyl-diazophosphonate
  作者：Igor D. Titanyuk、Irina P. Beletskaya、Alexander S. Peregudov、Sergey N. Osipov

  DOI：10.1016/j.jfluchem.2007.02.003

  日期：2007.7

  An efficient method for the preparation of α-(trifluoromethyl)-cyclopropylphosphonates and α-(trifluoromethyl)-1,2-epoxyphosphonates has been developed. The method is based on metal-catalyzed reaction of diethyl 1-diazo-2,2,2-trifluoroethylphosphonate (1) with alkenes or carbonyl compounds, respectively. It established an essential advantage of CuI-catalysis over Rh2(OAc)4 in cyclopropanation reactions

  已经开发了制备α-（三氟甲基）-环丙基膦酸酯和α-（三氟甲基）-1，2-环氧膦酸酯的有效方法。该方法基于1-重氮-2,2,2-三氟乙基膦酸二乙酯（1）分别与烯烃或羰基化合物的金属催化反应。在环丙烷化反应中，它建立了CuI催化相对于Rh 2（OAc）4的重要优势。廉价的碘化铜在环氧膦酸酯（3）的合成中也表现出良好的催化活性。
• Copper-catalyzed reactions of 1-tert-butyloxycarbonyl-substituted gramine with diazo compounds
  作者：D. V. Vorobyeva、T. P. Vasilyeva、S. N. Osipov

  DOI：10.1007/s11172-022-3613-0

  日期：2022.9

  Copper-catalyzed reactions of N-Boc-gramine with diazo compounds have been studied. In the case of ethyl diazoacetate, an indoline derivative with an exocyclic double bond is formed due to a [2,3]-sigmatropic rearrangement. The reaction of N-Boc-gramine with CF3-substituted diazo compounds, viz., diazocarboxylate and diazophosphonate, proceeds via a [1,2]-sigmatropic rearrangement with the formation of new derivatives of tryptophan and its P analogue.

  研究人员对 N-Boc-gramine 与重氮化合物的铜催化反应进行了研究。在重氮乙酸乙酯的反应中，由于发生了[2,3]-对位重排，形成了具有外环双键的吲哚啉衍生物。N-Boc-gramine 与 CF3 取代的重氮化合物（即重氮羧酸酯和重氮膦酸酯）通过 [1,2]-σmatropic 重排反应生成了色氨酸及其 P 类似物的新衍生物。
• Orally Bioavailable Small-Molecule CD73 Inhibitor (OP-5244) Reverses Immunosuppression through Blockade of Adenosine Production
  作者：Xiaohui Du、Jared Moore、Brian R. Blank、John Eksterowicz、Dena Sutimantanapi、Natalie Yuen、Todd Metzger、Brenda Chan、Tom Huang、Xi Chen、Yuping Chen、Frank Duong、Wayne Kong、Jae H. Chang、Jessica Sun、Tatiana Zavorotinskaya、Qiuping Ye、Melissa R. Junttila、Chudi Ndubaku、Lori S. Friedman、Valeria R. Fantin、Daqing Sun

  DOI：10.1021/acs.jmedchem.0c01086

  日期：2020.9.24

  The adenosinergic pathway represents an attractive new therapeutic approach in cancer immunotherapy. In this pathway, ecto-5-nucleotidase CD73 has the unique function of regulating production of immunosuppressive adenosine (ADO) through the hydrolysis of AMP. CD73 is overexpressed in many cancers, resulting in elevated levels of ADO that correspond to poor patient prognosis. Therefore, reducing the level of ADO via inhibition of CD73 is a potential strategy for treating cancers. Based on the binding mode of adenosine 5'-(alpha,beta-methylene)-diphosphate (AOPCP) with human CD73, we designed a series of novel monophosphonate small-molecule CD73 inhibitors. Among them, OP-5244 (35) proved to be a highly potent and orally bioavailable CD73 inhibitor. In preclinical studies, 35 completely inhibited ADO production in both human cancer cells and CD8(+) T cells. Furthermore, 35 lowered the ratio of ADO/AMP significantly and reversed immunosuppression in mouse models, indicating its potential as an in vivo tool compound for further development.
• Synthesis of α-trifluoromethyl-α-hydroxycarboxylate dervatives and their phosphorus-containing analogs with the use of fluorinated diazo compounds
  作者：I. D. Titanyuk、D. V. Vorob’eva、S. N. Osipov、I. P. Beletskaya

  DOI：10.1134/s1070428010050015

  日期：2010.5

  Approach was developed underlain by the use of fluorinated diazocompounds to the synthesis of derivatives of alpha-trifluoromethyl-alpha-hydroxycarboxylic acids and their phosphorus-containing analogs, alpha-trifluoromethyl-alpha-hydroxyphosphonic acids. Methyl 2-diazo-3,3,3-trifluoropropionate and diethyl 1-diazo-2,2,2-trifluoroethylphosphonate under the action of catalytic quantities of dirhodium tetraacetate Rh-2(OAc)(4) easily inserted into the O-H bond leading to the formation of the corresponding products in high yields.