diethyl ((E)-1,3-pentadienyl)phosphonate | 67221-20-9

• 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 ((E)-1,3-pentadienyl)phosphonate
• 英文别名: diethyl ((1E,3E)-penta-1,3-dien-1-yl)phosphonate；(1E,3E)-pentadienylphosphonate；(1E,3E)-diethyl-penta-1,3-dienylphosphonate；diethyl (1E,3E)-penta-1,3-dienylphosphonate；diethyl (E)-1,3,7-pentadienylphosphonate；(1E,3E)-1-diethoxyphosphorylpenta-1,3-diene
• CAS: 67221-20-9
• 化学式: C₉H₁₇O₃P
• 分子量: 204.206
• InChiKey: OGJVWSFHBXWSJO-NUXDXBQRSA-N

物化性质

• 沸点：
  82-84 °C(Press: 0.01 Torr)
• 密度：
  1.014±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diethyl ((E)-1,3-pentadienyl)phosphonate 在 甲醇 、 (+)-1,2-双((2S,5S)-2,5-二苯基膦)乙烷 、 copper(l) chloride 、 zinc dibromide 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 40.5h， 生成 diethyl [(2R,3S)-3-hydroxy-2-((E)-propenyl)octyl]phosphonate
  参考文献：
  名称：

  铜（I）催化的α，β，γ，δ-不饱和膦酸酯的对映选择性1,6-硼化

  摘要：

  使用（S，S）-Ph-BPE作为手性配体，得到铜（I）催化的1，3-二烯基膦酸酯的不对称1，6-硼酸酯化。区域，立体和对映体选择性硼化成功地进行，得到了含膦酸酯的烯丙基硼酸酯，具有高达97％ee的高对映体选择性。所得产物的进一步应用产生了有价值的γ-丁内酯的膦酸酯类似物。

  DOI：

  10.1021/acs.orglett.8b03532
• 作为产物：
  描述：

  diethyl pent-1-ynylphosphonate 在 四(三苯基膦)钯 作用下， 以 1,4-二氧六环 为溶剂， 反应 3.5h， 以83%的产率得到diethyl ((E)-1,3-pentadienyl)phosphonate
  参考文献：
  名称：

  Isomerization of Diethyl 1-Alkynylphosphonates to 1,3-Dienylphosphonates Followed by Diels-Alder Reaction with Dead, Maleic Anhydride and Maleimide

  摘要：

  Isomerization of diethyl 1-alkynylphosphonates, 1, with Pd[(PPh)(3)](4) in refluxing 1,4-dioxane provides 1,3-dienylphosphonates, 2, in satisfactory to excellent isolated yield (45-83%). The reaction is tolerant of chlorides and cyclic substituents. Cycloaddition reaction of 2 with DEAD provided the corresponding diethyl 3-(diethoxyphosphoryl)-6-alkyl-3,6-dihydropyridazine-1,2-dicarboxylates, 3, in 85% isolated yield. The cycloaddition products can be obtained in a one-pot reaction directly from the isomerized 1-alkynylphosphonates with no loss in yields. Similarly, 1,3-dioxo-1,3,3a,4,7,7a-hexahydroisobenzofuran-4-ylphosphonate, and 1,3-dioxo-2,3,3a,4,7,7a-hexahydro-1H-isoindo1-4-ylphosphonate 4 were obtained by reacting 1,3-dienylphosphonates with maleic anhydride and maleimide respectively.

  DOI：

  10.3987/com-10-s(e)12

文献信息

• An Efficient and Facile Access to Substituted 1<i>E</i>,3<i>E</i>-Dienylphosphonates<i>via</i>Horner-Wadsworth-Emmons Olefination of α,β-Unsaturated Aldehydes with Tetraethyl Methylenebisphosphonate
  作者：Marwa Yahyaoui、Soufiane Touil、Ali Samarat

  DOI：10.1246/cl.180149

  日期：2018.6.5

  operationally simple and high-yielding synthetic method for 1E,3E-dienylphosphonates has been developed through the Horner-Wadsworth-Emmons olefination of α,β-unsaturated aldehydes with tetraethyl methylenebisphosphonate, in heterogeneous medium, in the presence of solid potassium carbonate, in refluxing DMF.

  通过 α,β-不饱和醛与亚甲基双膦酸四乙酯的 Horner-Wadsworth-Emmons 烯化，在非均相介质中，在固体碳酸钾存在下，开发了一种操作简单且高产的 1E,3E-二烯基膦酸酯合成方法。回流 DMF。
• Synthesis of Phosphonomethyl Tetrahydrofurans via the Mori–Tamaru Reaction of Phosphonodienes
  作者：Rishi R. Paudel、Jeremy N. Ridenour、Nigam P. Rath、Christopher D. Spilling

  DOI：10.1021/acs.orglett.0c01080

  日期：2020.5.15

  (the Mori-Tamaru reaction) gives hydroxy vinyl phosphonates in good yields with excellent control of the relative stereochemistry. Base-induced cyclization of the vinyl phosphonates yields phosphonomethyl-substituted tetrahydrofurans. Inversion of the hydroxyl stereochemistry by Mitsunobu reaction and then cyclization yields a different set of phosphonomethyl-substituted tetrahydrofuran diastereoisomers

  镍催化的膦酰基二烯还原至醛的还原反应（Mori-Tamaru反应）可很好地控制相对立体化学，从而获得高产率的羟基乙烯基膦酸酯。碱诱导的乙烯基膦酸酯的环化产生膦酰基甲基取代的四氢呋喃。通过Mitsunobu反应反转羟基立体化学，然后环化，得到另一组膦酰基甲基取代的四氢呋喃非对映异构体。
• Conjugate addition of lithiated Schöllkopf's bislactim ether to 1E,3E-butadienylphosphonates: Stereocontrolled access to 2,3-anti-4E 2-amino-6-phosphono-4-hexenoic acid derivatives
  作者：Vicente Ojea、Susana Conde、María Ruiz、Ma Carmen Fernández、JoséMa Quintela

  DOI：10.1016/s0040-4039(97)00888-5

  日期：1997.6

  Face-selective 1,6-addition of lithiated Schöllkopf's bislactime ether 5 to 4-substituted, 1,4- or 3,4-disubstituted 1E,3E-butadienylphosphonates6a-d allows a direct and stereocontrolled access to semi-rigid AP6 analogues, the 2,3-anti-4E 2-amino-6-phosphono-4-hexenoic acid derivatives 4a-c. The relative stereochemistry was assigned from a NMR study of the cyclic derivative 12c. Ten-membered trans-fused

  将锂化的Schöllkopf's bislactime醚5选择性添加到4-取代的1,4或3,4-二取代的1 E，3 E-丁二烯基膦酸酯6a-d上，可以通过面选择性地直接和立体控制地进入半刚性AP6类似物，即2，3-抗-4 E 2-氨基-6-膦酰基-4-己酸衍生物4a-c。从环状衍生物12c的NMR研究确定了相对立体化学。调用十元反式融合的椅子-船状过渡态，以使添加的立体化学结果合理化。
• Phosphonates useful as modulators of T-gamma-9-delta-2 activity
  申请人：Montero Jean-Louis

  公开号：US20100204184A1

  公开（公告）日：2010-08-12

  The invention concerns novel phosphonate derivatives, preparation method, use thereof as ligands modulating T γ9δ2 lymphocyte activity and pharmaceutical compositions comprising them.

  这项发明涉及新型膦酸盐衍生物、其制备方法，以及将其用作调节T γ9δ2淋巴细胞活性的配体和包含它们的制药组合物。
• Synthesis of Prenyl Pyrophosphonates as New Potent Phosphoantigens Inducing Selective Activation of Human Vγ9Vδ2 T Lymphocytes
  作者：Ibrahim Zgani、Chantal Menut、Michel Seman、Valerie Gallois、Virginie Laffont、Jeanine Liautard、Jean-Pierre Liautard、Marc Criton、Jean-Louis Montero

  DOI：10.1021/jm049861z

  日期：2004.8.1

  gamma9delta2T cells represent the most abundant population of human blood gammadeltaT lymphocytes. They produce and promote strong cytotoxic activity against many pathogens that are implicated in several human infectious diseases. Their activation requires their exposure to small phosphorus-containing antigens in the family of prenyl pyrophosphates and their related biosynthetic precursors such as isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP), which are naturally occurring metabolites in mycobacteria and several other microbial pathogens. The broad specificity in the recognition of these molecules by the T-lymphocyte population expressing a Vgamma9Vdelta2 cell receptor might facilitate their manipulation by designing small potent synthetic agonist ligands. In this paper, we describe the synthesis and the biological evaluation of new pyrophosphonate compounds as new isosteric analogues of natural prenyl pyrophosphates. Several prenyl and alkenyl pyrophosphonate with different chain lengths and degrees of insaturation (24-28, 48-50, and 64-66) were tested as well as the alkoxymethylpyrophosphonic analogue of IPP (compound 76) as its closest isostere. Several of them appeared to be better activators of Vgamma9Vdelta2 T cell proliferation than IPP. These results open the perspective of a potential use of isoprenoides pyrophosphonates as specific immunoregulatory molecules.