diethyl ((E)-1,3-butadienyl)phosphonate

• 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-butadienyl)phosphonate
• 英文别名: 1-(diethylphosphono)-1,3-butadiene；diethyl (E)-buta-1,3-dienylphosphonate；(1E)-1-diethoxyphosphoryl-buta-1,3-diene；(1E)-1-diethoxyphosphorylbuta-1,3-diene
• 化学式: C₈H₁₅O₃P
• 分子量: 190.179
• InChiKey: CIMBBEFERGFJOG-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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-butadienyl)phosphonate 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(E)-buta-1,3-dienylphosphonic acid
  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：

  trans-1-chloro-4-diethoxyphosphorylbutene 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 以27 g的产率得到diethyl ((E)-1,3-butadienyl)phosphonate
  参考文献：
  名称：

  A Practical Synthesis of 3-Diethoxyphosphoryl-1,2-pyridazine Derivatives

  摘要：

  在微波 (MW) 加热下，1-二乙氧基磷酰基丁-1,3-二烯环加成至偶氮二甲酸二乙酯、二异丙酯和二叔丁酯，以优异的收率生成相应的杂狄尔斯-阿尔德 (HD-A) 环加合物。使用六入口平行合成转子（>10 g规模）可以方便地放大二叔丁基衍生物的环加成反应。 B3LYP/6-31G** 计算证实了该反应的协调但高度异步的特征。二叔丁氧羰基环加合物与正交脱保护相容（即，选择性N-脱保护而不降解膦酸酯）。因此，该环加合物的C=C键的还原和二羟基化，然后TFA脱保护，分别得到3-二乙氧基磷酰基六氢-1,2-哒嗪和3-二乙氧基磷酰基-4,5-二羟基六氢-1,2-哒嗪。这种 HD-A 策略为外消旋系列的环状 α-肼酸和 azafagomine 衍生物的膦酸盐生物电子等排体提供了便捷的途径。

  DOI：

  10.1055/s-0028-1088056

文献信息

• New and Efficient Synthesis of 1,3-Dienylphosphonates by Palladium-Catalyzed Substitution of Propargylic Esters to Diethyl Phosphite
  作者：Xiao-Ning Liu、Wei-Lei Guo、Chuan-Jin Hou、Xiang-Ping Hu

  DOI：10.1080/00397911.2012.725795

  日期：2013.10.2

  Abstract An efficient route to the synthesis of 1,3-dienylphosphonates (1) has been developed for the first time by the substitution of propargylic esters (2) to the diethyl phosphite (3) nucleophile in the presence of Pd2(dba)3 · CHCl3 (2 mol %) and 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (4 mol%). Both the alkyl and aryl 1,3-dienylphosphonates can be prepared from this transformation. Supplemental

  摘要 通过在 Pd2(dba)3 存在下将炔丙酯 (2) 取代为亚磷酸二乙酯 (3) 亲核试剂，首次开发了合成 1,3-二烯基膦酸酯 (1) 的有效途径。 CHCl3 (2 mol%) 和 2,2'-双(二苯基膦)-1,1'-联萘 (4 mol%)。烷基和芳基 1,3-二烯基膦酸酯均可从该转化制备。补充材料可用于本文。转至出版商的 Synthetic Communications® 在线版以查看免费的补充文件。图形概要
• Polycyclic phosphonic acid derivatives obtained by a [4+2] cycloaddition strategy using phosphonodienes
  作者：Elise Villemin、Koen Robeyns、Raphael Robiette、Marie-France Herent、Jacqueline Marchand-Brynaert

  DOI：10.1016/j.tet.2012.11.059

  日期：2013.1

  A practical route is described for the preparation of 1-phosphono-3(4-di)-substituted-1,3-butadienes based on the Horner–Wadsworth–Emmons (HWE) reaction. Their reactivity in the Diels–Alder (DA) reaction with three selected dienophiles is studied and compared to diethyl 1-phosphono-1,3-butadiene. A particular attention is given to the P-deprotection of cycloadducts from dibenzyl phosphonodienes. New

  描述了一种基于Horner-Wadsworth-Emmons（HWE）反应制备1-膦酰基3（4-di）-取代的1，，3-丁二烯的实用方法。研究了它们与三种选定的亲二烯体在狄尔斯-阿尔德（DA）反应中的反应性，并将其与1-乙基膦酰基-1,3-丁二烯二乙基酯进行了比较。特别注意从二苄基膦酰基二烯对环加合物进行P-脱保护。使用这种HWE / DA反应序列，已经获得了新的磷酸化自行车和三轮车。
• <scp>Pd‐Catalyzed</scp> Asymmetric Synthesis of 3, <scp>4‐Dihydroisoquinolinones</scp> From <scp> <i>N</i> ‐Ts‐Benzamides </scp> and 1, <scp>3‐Dienes</scp>
  作者：Tae Kyun Kim、So Won Youn

  DOI：10.1002/bkcs.12227

  日期：2021.3

  A Pd(II)‐catalyzed asymmetric oxidative annulation of N‐Ts‐benzamides with 1,3‐dienes using a chiral pyridine‐oxazoline‐type ligand for the regio‐ and stereoselective synthesis of chiral 3,4‐dihydroisoquinolinones has been developed.

  已经开发了一种Pd（II）催化的N -Ts-苯甲酰胺与1,3-二烯的不对称氧化环合反应，使用手性吡啶-恶唑啉型配体进行手性3,4-二氢异喹啉酮的区域和立体选择性合成。
• 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。
• Cobalt Catalyzed Reductive Spirocyclopropanation Reactions
  作者：Jacob Werth、Kristen Berger、Christopher Uyeda

  DOI：10.1002/adsc.201901293

  日期：2020.1.23

  partners including those containing sulfur and nitrogen heterocycles. An example of an intramolecular Rh‐catalyzed [5+2]‐cycloaddition of a vinyl spirocyclopropane is demonstrated, providing rapid access to a complex tricyclic framework. Overall, this catalyst system is capable of suppressing the kinetically facile 1,2‐hydride shift, which has hampered the development of Simmons−Smith reactions using

  吡啶吡啶-二亚胺钴（PDI）络合物催化末端1,3-二烯的还原螺环丙烷化。宝石-二氯环烷烃可作为卡宾的前体，而锌则用作末端电子源。该反应对许多宝石-二氯伙伴有效，包括那些含有硫和氮杂环的伙伴。展示了分子内Rh催化的乙烯基螺环丙烷的[5 + 2]-环加成反应的一个实例，可快速进入复杂的三环骨架。总体而言，该催化剂体系能够抑制动力学上较容易的1,2-氢化物移位，这阻碍了使用具有β-氢原子的Zn类胡萝卜素的Simmons-Smith反应的发展。