4-((diethoxyphosphoryl)difluoromethyl)phenyl trifluoromethanesulfonate | 181188-34-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-((diethoxyphosphoryl)difluoromethyl)phenyl trifluoromethanesulfonate
• 英文别名: 4-(Trifluoromethylsulfonyloxy)-alpha,alpha-difluorobenzylphosphonic acid diethyl ester；[4-[diethoxyphosphoryl(difluoro)methyl]phenyl] trifluoromethanesulfonate
• CAS: 181188-34-1
• 化学式: C₁₂H₁₄F₅O₆PS
• 分子量: 412.271
• InChiKey: OBIKAYAMPMZMNA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  87.3
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  4-((diethoxyphosphoryl)difluoromethyl)phenyl trifluoromethanesulfonate 在 bis-triphenylphosphine-palladium(II) chloride 盐酸 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.33h， 生成 2-{4'-[(Diethoxyphosphoryl)difluoromethyl]phenyl}-5-furan-carbaldehyde
  参考文献：
  名称：

  Facile syntheses of building blocks for the construction of phosphotyrosine mimetics

  摘要：

  横松和渋谷描述的铜催化锌膦酸酯化学可用于通过斯蒂尔（Stille）和铃木-宫浦（Suzuki-Miyaura）偶联反应进入经典的金属有机偶联反应领域。1,4-二碘苯在铜(I)催化下与由二乙基溴二氟甲基膦酸酯衍生的有机锌试剂发生偶联，生成二乙基(4-碘苯基)二氟甲基膦酸酯。与(4-三氟甲磺酰氧基)和(4-九氟丁磺酰氧基)碘苯进行的偶联反应产率更高。碘化物和三氟甲磺酸酯在钯催化条件下与一系列锡烷和硼酸发生偶联，产率从中等到优异。渋谷-横松偶联反应在具有更丰富官能团的碘芳烃和杂芳烃上也取得了成功，这些重要磷酸类似物被引入多种骨架上。

  DOI：

  10.1039/b004187o
• 作为产物：
  描述：

  4-碘苯酚 在 吡啶 、 copper(I) bromide 、 锌 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 4-((diethoxyphosphoryl)difluoromethyl)phenyl trifluoromethanesulfonate
  参考文献：
  名称：

  Facile syntheses of aryldifluorophosphonate building blocks

  摘要：

  The copper-catalysed zinc phosphonate chemistry described by Yokomatsu and Shibuya can be used directly in the synthesis of phosphotyrosine analogue F(2)Pmp, and in entering the classical organometallic coupling repertoire via Stille and Suzuki-Miyaura couplings. Herein, we report a streamlined synthesis of F(2)Pmp, and of a pivotal triflate, which undergoes a range of palladium-catalysed couplings with aryl and heteroaryl components. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00266-x

文献信息

• Synthesis and biological evaluation of α,α-difluorobenzylphosphonic acid derivatives as small molecular inhibitors of protein-tyrosine phosphatase 1B
  作者：Tsutomu Yokomatsu、Tetsuo Murano、Ikuko Umesue、Shinji Soeda、Hiroshi Shimeno、Shiroshi Shibuya

  DOI：10.1016/s0960-894x(99)00027-x

  日期：1999.2

  series of alpha,alpha-difluorobenzylphosphonic acids having a hydrophobic functional group were prepared via the Stille coupling reaction from halogenated alpha,alpha-difluorobenzylphosphonates. Evaluation of inhibitory activity toward protein tyrosine phosphatase (PTP 1B) revealed that the ethynyl, phenylethynyl and (E)-styryl groups on the benzene nuclei increased the inhibitory activity of alpha,alph

  通过Stille偶联反应，由卤化的α，α-二氟苄基膦酸酯制备了一系列具有疏水性官能团的α，α-二氟苄基膦酸。对蛋白酪氨酸磷酸酶（PTP 1B）的抑制活性的评估表明，苯核上的乙炔基，苯基乙炔基和（E）-苯乙烯基增加了α，α-二氟苄基膦酸的抑制活性。将（E）-苯乙烯基和双甲基磺酰胺官能团同时引入到α，α-二氟苄基膦酸的苯核上时，抑制活性显着提高。
• Nickel‐Catalyzed Cross‐Coupling of Bromodifluoromethylphosphonates with Arylboron Reagents
  作者：Masami Kuriyama、Genki Maeda、Kazuya Kamata、Yusuke Kodama、Kosuke Yamamoto、Osamu Onomura

  DOI：10.1002/adsc.202201140

  日期：2023.1.10

  The nickel-catalyzed cross-coupling of bromodifluoromethylphosphonates with arylboron reagents was developed with a 1,10-phenanthroline-type ligand. In this process, functionalized and heterocycle-containing boroxines were found to be suitable partners, and the catalytic modification of biologically active molecules, such as fenofibrate and indomethacin, was also successfully achieved. Furthermore

  溴二氟甲基膦酸酯与芳基硼试剂的镍催化交叉偶联是用 1,10-菲咯啉型配体开发的。在此过程中，发现功能化和含杂环的环硼氧嘧啶是合适的合作伙伴，并成功实现了非诺贝特和吲哚美辛等生物活性分子的催化修饰。此外，克级反应顺利进行，以高产率得到所需产物。
• Facile syntheses of aryldifluorophosphonate building blocks
  作者：G.Stuart Cockerill、Howard J. Easterfield、Jonathan M. Percy

  DOI：10.1016/s0040-4039(99)00266-x

  日期：1999.3

  The copper-catalysed zinc phosphonate chemistry described by Yokomatsu and Shibuya can be used directly in the synthesis of phosphotyrosine analogue F(2)Pmp, and in entering the classical organometallic coupling repertoire via Stille and Suzuki-Miyaura couplings. Herein, we report a streamlined synthesis of F(2)Pmp, and of a pivotal triflate, which undergoes a range of palladium-catalysed couplings with aryl and heteroaryl components. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Facile syntheses of building blocks for the construction of phosphotyrosine mimetics
  作者：G. Stuart Cockerill、Howard J. Easterfield、Jonathan M. Percy、Stéphane Pintat

  DOI：10.1039/b004187o

  日期：——

  The copper-catalysed zinc phosphonate chemistry described by Yokomatsu and Shibuya can be used to enter the classical organometallic coupling repertoire via Stille and Suzuki–Miyaura couplings. 1,4-Diiodobenzene underwent coupling with the organozinc reagent derived from diethyl bromodifluoromethylphosphonate with copper(I) catalysis to afford diethyl (4-iodophenyl)difluoromethylphosphonate. Higher yielding couplings were run with (4-trifluoromethylsulfonyloxy)- and (4-nonafluorobutylsulfonyloxy)-iodobenzenes. The iodide and the triflate coupled under palladium-catalysed conditions with a range of stannanes and boronic acids in moderate to excellent yields. Shibuya–Yokomatsu couplings were also successful with more functionalised iodoarenes and heteroarenes presenting the important phosphate mimic on a range of scaffolds.

  横松和渋谷描述的铜催化锌膦酸酯化学可用于通过斯蒂尔（Stille）和铃木-宫浦（Suzuki-Miyaura）偶联反应进入经典的金属有机偶联反应领域。1,4-二碘苯在铜(I)催化下与由二乙基溴二氟甲基膦酸酯衍生的有机锌试剂发生偶联，生成二乙基(4-碘苯基)二氟甲基膦酸酯。与(4-三氟甲磺酰氧基)和(4-九氟丁磺酰氧基)碘苯进行的偶联反应产率更高。碘化物和三氟甲磺酸酯在钯催化条件下与一系列锡烷和硼酸发生偶联，产率从中等到优异。渋谷-横松偶联反应在具有更丰富官能团的碘芳烃和杂芳烃上也取得了成功，这些重要磷酸类似物被引入多种骨架上。