(+/-)-dibenzyl [hydroxy(4-nitrophenyl)methyl]phosphonate

• 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: (+/-)-dibenzyl [hydroxy(4-nitrophenyl)methyl]phosphonate
• 英文别名: dibenzyl 1-hydroxy-1-(4-nitrophenyl)methylphosphonate；Bis(phenylmethoxy)phosphoryl-(4-nitrophenyl)methanol
• 化学式: C₂₁H₂₀NO₆P
• 分子量: 413.367
• InChiKey: XXKLSUWKSZWEMF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (+/-)-dibenzyl [hydroxy(4-nitrophenyl)methyl]phosphonate 在 palladium 10% on activated carbon 、 氢气 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、1.0 MPa 条件下， 反应 3.5h， 以50%的产率得到1-(4-aminophenyl)-1-hydroxymethylphosphonic acid
  参考文献：
  名称：

  α-羟基膦酸二苄酯和α-羟基膦酸的绿色合成及细胞毒活性

  摘要：

  AbstractA series of dibenzyl α‐hydroxyphosphonates and the corresponding α‐hydroxyphosphonic acids, mostly new compounds, have been synthesized. The dibenzyl α‐hydroxyphosphonates have been obtained in the Pudovik reaction of substituted benzaldehydes and dibenzyl phosphite in the presence of triethylamine as the catalyst. The amount of the solvent was minimized during the reaction, and the workup involved crystallization from the reaction mixture. A new protocol was developed to transform the dibenzyl 1‐hydroxyphosphonates to the corresponding phosphonic acids by catalytic hydrogenation. The derivatives prepared were screened as potential cytotoxic agents against Mes‐Sa human uterine sarcoma cell line.

  DOI：

  10.1002/hc.21436
• 作为产物：
  描述：

  亚磷酸二苄酯 、 对硝基苯甲醛 在 Nafion-supported oxovanadium catalyst 作用下， 以 neat (no solvent) 为溶剂， 反应 20.0h， 以90%的产率得到(+/-)-dibenzyl [hydroxy(4-nitrophenyl)methyl]phosphonate
  参考文献：
  名称：

  在无溶剂条件下，Nafion®支持的氧钒催化醛的羰基化反应

  摘要：

  可以通过离子交换方法轻松地制备Nafion®树脂负载的氧钒（IV）催化剂。将该固体钒基全氟化磺酸盐催化剂用作在室温下无溶剂条件下各种醛的氢膦酰化的有效且可回收的催化剂。可以通过简单的过滤来回收催化剂，并在不显着降低活性的情况下对其进行再利用。版权所有©2012 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/aoc.2879

文献信息

• Rational synthesis of α-hydroxyphosphonic derivatives including dronic acids
  作者：Alajos Grün、Zita Rádai、Dávid Illés Sőregi-Nagy、István Greiner、György Keglevich

  DOI：10.1080/10426507.2018.1555537

  日期：2019.5.27

  Abstract New, green methods have been elaborated for the syntheses of α-hydroxyphosphonates and α-hydroxymethylenebisphosphonic derivatives (HMBPs, dronates). α-Hydroxyphosphonates were prepared via the Pudovik reaction, while the synthesis of HMBPs has been performed in the three-component reaction of carboxylic acids, phosphorus trichloride and phosphorus acid. Graphical Abstract

  摘要 α-羟基膦酸酯和α-羟基亚甲基双膦酸衍生物（HMBPs，膦酸酯）的合成新的、绿色的方法已经被阐述。α-羟基膦酸酯是通过Pudovik反应制备的，而HMBPs的合成是在羧酸、三氯化磷和磷酸的三组分反应中进行的。图形概要
• Organocatalytic enantioselective hydrophosphonylation of aldehydes
  作者：Juan V. Alegre-Requena、Eugenia Marqués-López、Pablo J. Sanz Miguel、Raquel P. Herrera

  DOI：10.1039/c3ob42403k

  日期：——

  our results concerning the first squaramide-catalysed hydrophosphonylation of aldehydes. In all cases, the reactions proceeded smoothly and cleanly under mild reaction conditions rendering final α-hydroxy phosphonates in very good yields and high enantioselectivities. It is one of the few organocatalytic examples of this reaction using aldehydes. It is the first time that diphenylphosphite (1e) has

  我们报告有关醛的第一个方胺催化的氢膦酰化反应的结果。在所有情况下，反应均在温和的反应条件下平稳而干净地进行，从而以非常好的收率和高对映选择性产生最终的α-羟基膦酸酯。它是使用醛的该反应的少数有机催化实例之一。与先前公开的方法中使用的亚磷酸二烷基酯相反，这是首次将亚磷酸二苯基酯（1e）成功用于醛的手性Pudovik反应中，从而扩大了这种不对称方法的通用性。
• Synthesis and anticancer cytotoxicity with structural context of an α-hydroxyphosphonate based compound library derived from substituted benzaldehydes
  作者：Zita Rádai、Tímea Windt、Veronika Nagy、András Füredi、Nóra Zsuzsa Kiss、Ivan Ranđelović、József Tóvári、György Keglevich、Gergely Szakács、Szilárd Tóth

  DOI：10.1039/c9nj02144b

  日期：——

  active clusters, which encouraged us to synthesize further dibenzyl-α-diphenyl-OPP derivatives that elicited pronounced cell killing. Further structure–activity relationships showed the relevance of hydrophobicity and the position of substituents on the main benzene ring as determinants of toxicity. The most active analogs proved to be equally, or even more toxic to the multidrug resistant (MDR) cell line

  我们合成了取代的苯甲醛衍生的α-羟基膦酸酯（αOHP），α-羟基膦酸（αOHPA）和α-膦酰氧基膦酸酯（αOPP），并表征了它们对一组癌细胞系的细胞毒性。使用基于荧光的细胞毒性试验，针对Mes-Sa亲本和Mes-Sa / Dx5多药耐药子宫肉瘤细胞系筛选了包含56个类似物的文库。细胞毒性筛选显示，二苄基-αOHP和二甲基-α-二苯基-OPP是最活跃的簇，这鼓励我们合成进一步的二苄基-α-二苯基-OPP衍生物，引起明显的细胞杀伤作用。进一步的结构-活性关系显示疏水性和主苯环上取代基的位置与毒性有关。事实证明，最活跃的类似物是同等的，
• Highly Enantioselective Aerobic Oxidation of α-Hydroxyphosphonates Catalyzed by Chiral Vanadyl(V) Methoxides Bearing <i>N</i>-Salicylidene-α-aminocarboxylates
  作者：Vijay D. Pawar、Sampada Bettigeri、Shiue-Shien Weng、Jun-Qi Kao、Chien-Tien Chen

  DOI：10.1021/ja060639o

  日期：2006.5.1

  An unprecedented vanadyl(V) methoxide complex 4 derived from 3,5-dibromo-N-salicylidene-l-tert-leucinate enables highly enantioselective aerobic oxidations of α-hydroxyphosphonates at ambient temperature with selectivity factors ranging from 3 to >99.

  一种前所未有的源自 3,5-二溴-N-水杨酸-1-叔亮氨酸盐的甲醇氧钒络合物 4 能够在环境温度下对 α-羟基膦酸酯进行高度对映选择性有氧氧化，选择性因子范围从 3 到 >99。