diethyl (4-methylpent-3-en-1-yl)phosphonate | 71071-57-3

• 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 (4-methylpent-3-en-1-yl)phosphonate
• 英文别名: 5-Diethoxyphosphoryl-2-methylpent-2-ene
• CAS: 71071-57-3
• 化学式: C₁₀H₂₁O₃P
• 分子量: 220.249
• InChiKey: LSXPUQFMKVWEEH-UHFFFAOYSA-N

物化性质

• 沸点：
  83-85 °C(Press: 1 Torr)
• 密度：
  0.983±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 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 (4-methylpent-3-en-1-yl)phosphonate 在 碘 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 正己烷 、 水 为溶剂， 反应 14.0h， 生成 α-phosphono-γ-iodoisopropyl-γ-butyrolactone
  参考文献：
  名称：

  Synthetic Route to a-Phosphono-g-butyrolactones: Synthesis of g-Substituted a-Methylene-g-butyro-lactones

  摘要：

  DOI：

  10.3987/com-96-7685
• 作为产物：
  描述：

  异戊烯醇 在 正丁基锂 、 三溴化磷 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 diethyl (4-methylpent-3-en-1-yl)phosphonate
  参考文献：
  名称：

  Synthesis of Prenyl Pyrophosphonates as New Potent Phosphoantigens Inducing Selective Activation of Human Vγ9Vδ2 T Lymphocytes

  摘要：

  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.

  DOI：

  10.1021/jm049861z

文献信息

• 8π Electrocyclic Reaction of Phosphonate Derivatives: Access to Seven-Membered Cross-Conjugated Cyclic Trienes
  作者：Hiroki Saito、Ranmaru Kato、Kazutada Ikeuchi、Takahiro Suzuki、Keiji Tanino

  DOI：10.1021/acs.orglett.1c03815

  日期：2021.12.17

  An anionic 8π electrocyclic reaction of 4-(diethoxyphosphoryl)-1,3,6-heptatriene derivatives was developed. Under the influence of a base, the substrate underwent deprotonation at the C5 position followed by the 8π electrocyclization of the resulting heptatrienyl anion. The subsequent Horner–Wadsworth–Emmons reaction in one pot, following the addition of an aldehyde, resulted in the production of the

  开发了 4-（二乙氧基磷酰基）-1,3,6-庚三烯衍生物的阴离子 8π 电环反应。在碱的影响下，底物在 C5 位置进行去质子化，然后对所得庚三烯阴离子进行 8π 电环化。在加入醛后，随后在一个锅中进行 Horner-Wadsworth-Emmons 反应，生成 3-亚烷基-1,4-环庚二烯衍生物。电环反应以立体定向的方式进行，导致两个相邻立体中心的立体控制形成。
• Phosphonates useful as modulators of t $g(g)9$g(d)2 lymphocyte activity
  申请人：Montero Jean-Louis

  公开号：US20060241087A1

  公开（公告）日：2006-10-26

  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酯衍生物，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药物组合物。
• One-pot Diels–Alder cycloaddition/gold(I)-catalyzed 6-<i>endo-dig</i> cyclization for the synthesis of the complex bicyclo[3.3.1]alkenone framework
  作者：Boubacar Sow、Gabriel Bellavance、Francis Barabé、Louis Barriault

  DOI：10.3762/bjoc.7.114

  日期：——

  The rapid synthesis of bicyclo[m.n.1]alkanone cores possessing quaternary carbon centers adjacent to a bridged ketone represents a significant synthetic challenge. This type of architectural feature is embedded in various complex biologically active compounds such as hyperforin and garsubellin A. Herein, we report a highly diastereoselective one-pot Diels–Alder reaction/Au(I)-catalyzed carbocyclization to generate bicyclo[3.3.1]alkanones in yields ranging from 48–93%.

  含有与桥接酮相邻的四价碳中心的bicyclo[m.n.1]烷酮核的快速合成代表着一个重要的合成挑战。这种结构特征嵌入在各种复杂的生物活性化合物中，如金丝桃素和加瑟贝林A。在这里，我们报告了一种高度对映选择性的一锅法Diels–Alder反应/Au(I)催化的碳环化反应，生成产率在48-93%之间的bicyclo[3.3.1]烷酮。
• 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。
• Phosphonylation of alkyl radicals
  作者：Junyue Yin、Xinru Lin、Linxiang Chai、Cheng-Yu Wang、Lin Zhu、Chaozhong Li

  DOI：10.1016/j.chempr.2023.03.016

  日期：2023.7

  remains elusive. Herein, we report the decarboxylative radical phosphonylation with trialkyl phosphites. Thus with the co-catalysis of 4DPAIPN (1,2,3,5-tetrakis(diphenylamino)-4,6-dicyanobenzene) and Cu(OAc)2, the visible light-induced reaction of redox-active esters of aliphatic carboxylic acids with trialkyl phosphites at room temperature provides the corresponding alkylphosphonates in satisfactory

  烷基膦酸酯在药物、农用化学品和材料科学中有着广泛的应用，其合成在有机化学中至关重要。虽然亲核和亲电 C(sp 3 )-膦酰化已有充分记录，但烷基的膦酰化仍然难以捉摸。在此，我们报道了亚磷酸三烷基酯的脱羧自由基膦酰化反应。因此，在 4DPAIPN (1,2,3,5-四(二苯氨基)-4,6-二氰基苯) 和 Cu(OAc) 2的共催化下，在室温下，脂肪族羧酸的氧化还原活性酯与亚磷酸三烷基酯发生可见光诱导反应，以令人满意的产率提供相应的烷基膦酸酯。该方案具有广泛的底物范围和广泛的官能团兼容性，能够实现复杂分子的后期修饰。提出了一种涉及烷基与 P(OR) 3的铜辅助偶联，然后对所得鏻中间体进行 Arbuzov 型脱烷基化的机制。