diethyl 3-methylbut-2-enylphosphonate | 51795-72-3

• 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 3-methylbut-2-enylphosphonate
• 英文别名: diethyl (3-methyl-2-butenyl)phosphonate；Diethyl (3-methylbut-2-en-1-yl)phosphonate；1-diethoxyphosphoryl-3-methylbut-2-ene
• CAS: 51795-72-3
• 化学式: C₉H₁₉O₃P
• 分子量: 206.222
• InChiKey: ROHAZABGEKHYAR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 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 3-methylbut-2-enylphosphonate 在 吡啶 、 三甲基溴硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以85%的产率得到3-甲基丁-2-烯基膦酸
  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
• 作为产物：
  描述：

  亚甲基二磷酸四乙酯 在 potassium tert-butylate sodium hydride 作用下， 以 二甲基亚砜 为溶剂， 反应 24.5h， 生成 diethyl 3-methylbut-2-enylphosphonate
  参考文献：
  名称：

  A facile route to allylic phosphonates via base-catalyzed isomerization of the corresponding vinylphosphonates

  摘要：

  DOI：

  10.1021/jo00065a021

文献信息

• Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts
  申请人：CALIFORNIA INSTITUTE OF TECHNOLOGY

  公开号：US09403854B2

  公开（公告）日：2016-08-02

  The invention pertains to the use of Group 8 transition metal carbene complexes as catalysts for olefin cross-metathesis reactions. In particular, ruthenium and osmium alkylidene complexes substituted with an N-heterocyclic carbene ligand are used to catalyze cross-metathesis reactions to provide a variety of substituted and functionalized olefins, including phosphonate-substituted olefins, directly halogenated olefins, 1,1,2-trisubstituted olefins, and quaternary allylic olefins. The invention further provides a method for creating functional diversity using the aforementioned complexes to catalyze cross-metathesis reactions of a first olefinic reactant, which may or may not be substituted with a functional group, with each of a plurality of different olefinic reactants, which may or may not be substituted with functional groups, to give a plurality of structurally distinct olefinic products. The methodology of the invention is also useful in facilitating the stereoselective synthesis of 1,2-disubstituted olefins in the cis configuration.

  该发明涉及将8族过渡金属卡宾配合物用作烯烃交叉⽐特⽅反应的催化剂。具体地，使用取代有N-杂环卡宾配体的钌和锇烷基亚烯配合物来催化交叉⽐特⽅反应，从而提供各种取代和官能化的烯烃，包括磷酸酯取代的烯烃，直接卤代的烯烃，1,1,2-三取代的烯烃和季铵烯烃。该发明还提供了一种利用上述配合物催化第一烯烃反应物（可能带有或不带有官能团）与多种不同烯烃反应物（可能带有或不带有官能团）进行交叉⽐特⽅反应，从而得到多种结构不同的烯烃产物的方法。该发明的方法还有助于促进顺式构型的1,2-二取代烯烃的立体选择性合成。
• 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。
• Palladium catalysed allylic acetoxylation of dialkyl allyl phosphonates.
  作者：Bruno Principato、Michel Maffei、Chhan Siv、Gérard Buono、Gilbert Peiffer

  DOI：10.1016/0040-4020(95)01046-7

  日期：1996.2

  The catalytic acetoxylation of dialkyl allyl phosphonates with the Pd(OAc)2/benzoquinone/MnO2/HOAc system leads, regioselectively, to dialkyl 3- acetoxy 1-alkenyl phosphonates. On the basis of the regio- and stereoselectivity of the reaction, a mechanism is proposed which involves a (π-allyl) palladium complex as intermediate.

  用Pd（OAc）2 /苯醌/ MnO 2 / HOAc体系催化二烷基烯丙基膦酸酯的乙酰氧基化，选择性地导致3-乙酰氧基1-链烯基膦酸二烷基酯。基于反应的区域选择性和立体选择性，提出了一种机理，该机理涉及（π-烯丙基）钯配合物作为中间体。
• Total Synthesis of (−)-Xishacorene B from (<i>R</i>)-Carvone Using a C–C Activation Strategy
  作者：Isabel Kerschgens、Alexander R. Rovira、Richmond Sarpong

  DOI：10.1021/jacs.8b05832

  日期：2018.8.8

  bond-forming processes, can offer new approaches to the synthesis of complex molecular scaffolds. In this Communication, we demonstrate the conversion of carvone to unusual bicyclo[3.3.1] and [3.2.1] frameworks by exploiting a Pd(0)-catalyzed C-C bond activation reaction and a radical cyclization process. This sequence is applied to a 10-step synthesis of the diterpene xishacorene B.

  传统上被视为无反应的 CC 键的活化，当与其他键形成过程相结合时，可以为复杂分子支架的合成提供新的方法。在这篇通讯中，我们通过利用 Pd(0) 催化的 CC 键活化反应和自由基环化过程证明了香芹酮向不寻常的双环 [3.3.1] 和 [3.2.1] 骨架的转化。该序列应用于二萜 xishacorene B 的 10 步合成。
• Unusual and efficient (Z)-stereoselective peterson synthesis of 2-diethoxyphosphonyl-1-alkoxy-3-methylpenta-1,3-dienes. Their use in the diels-alder reaction
  作者：Hashim Al-Badri、Elie About-Jaudet、Noël Collignon

  DOI：10.1016/0040-4039(96)00452-2

  日期：1996.4

  The lithiated anion of diethyl α-trimethylsilyl-prenylphosphonate, readily in situ generated from diethyl prenylphosphonate, reacts smoothly with various alkyl formates to give the title compounds with exclusive 1-(Z)-geometry and in high isolated yield. The [4 + 2] cycloaddition reaction of dienes 3 with electron-deficient dienophiles is described.

  α-三甲基甲硅烷基异戊二烯基膦酸二乙酯的锂化阴离子易于原位生成，由二乙基异戊二烯基膦酸酯与各种烷基形式平稳反应，得到具有独特的1-（Z）几何形状且分离产率高的标题化合物。描述了二烯3与缺乏电子的亲二烯体的[4 + 2]环加成反应。