diethyl 1,2-dihydroxy-2-phenylethanephosphonate

• 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 1,2-dihydroxy-2-phenylethanephosphonate
• 英文别名: (1S,2S)-1-diethoxyphosphoryl-2-phenylethane-1,2-diol
• 化学式: C₁₂H₁₉O₅P
• 分子量: 274.254
• InChiKey: MNUXTVDHOBJIBM-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl 1,2-dihydroxy-2-phenylethanephosphonate 在 水 、 碳酸氢钠 作用下， 以 甲醇 为溶剂， 以84%的产率得到2-羟基苯乙酮
  参考文献：
  名称：

  A Stereoselective Synthetic Route to (E)-2-Arylvinylphosphonates

  摘要：

  末端炔1与Cp2Zr(H)Cl（Cp = η⁵-C₅C₅）反应生成有机锆（IV）配合物2，这些配合物与二烷基氯代磷酸酯反应得到（E）-芳基乙烯基膦酸酯3。

  DOI：

  10.1055/s-1999-2727
• 作为产物：
  描述：

  diethyl benzyloxymethylphosphonate 在 RuCl[(1R,2R)-p-TsNCH(C6H5)CH-(C6H5)NH2](η6-benzene) 、 palladium 10% on activated carbon 、 氢气 、 溶剂黄146 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 32.92h， 生成 diethyl 1,2-dihydroxy-2-phenylethanephosphonate
  参考文献：
  名称：

  基于动态动力学拆分的α-烷氧基-β-酮膦酸酯的不对称转移加氢。单保护的1,2-二羟基膦酸酯的非对映和对映选择性合成

  摘要：

  观察到由动态动力学拆分驱动的各种2-取代的α-烷氧基-β-酮膦酸酯3的不对称转移氢化反应有效地进行，得到了相应的2-取代的α-烷氧基-β-羟基膦酸酯4。非对映和对映选择性。通过使用定义明确的可商购的手性过渡金属催化剂以及甲酸和三乙胺的0.2：1混合物作为氢源和溶剂，可以促进这些过程。

  DOI：

  10.1021/jo500148j

文献信息

• Osmium-Catalyzed Dihydroxylation of Olefins in Acidic Media: Old Process, New Tricks
  作者：Philippe Dupau、Robert Epple、Allen??A. Thomas、Valery??V. Fokin、K.??Barry Sharpless

  DOI：10.1002/1615-4169(200206)344:3/4<421::aid-adsc421>3.0.co;2-f

  日期：2002.6

  osmium-catalyzed dihydroxylation has uncovered that electron-deficient olefins are converted into the corresponding diols much more efficiently when the pH of the reaction medium is maintained on the acidic side. Further studies have identified citric acid as the additive of choice, for it allows preparation of very pure diols in yields generally exceeding 90%. As described here, a much wider range of olefin classes

  对锇催化的二羟基化中 500 多种不同功能化添加剂的筛选发现，当反应介质的 pH 值保持在酸性时，缺电子烯烃转化为相应二醇的效率更高。进一步的研究已将柠檬酸确定为首选添加剂，因为它可以制备非常纯的二醇，产率通常超过 90%。正如这里所描述的，现在可以成功地对更广泛的烯烃类别进行二羟基化。该过程在实验上很简单，在大多数情况下，只需将反应物溶解在水或水/叔丁醇混合物中，搅拌它们，然后过滤出纯二醇产物。
• Stereochemical aspects of the asymmetric synthesis of chiral α,β-dihydroxy phosphonates. Synthesis of α,β-dihydroxy phosphonic acids
  作者：Alessandro Bongini、Roberto Camerini、Mauro Panunzio、Elisa Bandini、Giorgio Martelli、Giuseppe Spunta

  DOI：10.1016/s0957-4166(96)00456-9

  日期：1996.12

  The nature of the O-protecting group is crucial to obtain, in terms of diastereoselectivity and chemical yields, the best results. An ab initio molecular orbital study on 2-silyloxy propanal and MM2 studies on 2-alkoxy propanal show the existence of stable cyclic and acyclic conformers, which are presumably responsible for the high syn diastereoselectivity observed in the addition of non-metal carrying

  从手性醛开始已经获得了经由有机亚磷酸酯对醛的不对称膦酰化进行立体控制。就非对映选择性和化学产率而言，O-保护基团的性质对于获得最佳结果至关重要。一个从头算分子轨道研究2甲硅烷氧基丙醛和MM2研究上的2-烷氧基丙醛显示稳定环状和无环的构象，这大概是负责高的存在顺式在加入非承载的金属亚磷酸酯的非对映选择性观察。
• Enantioselective synthesis of threo-α,β-dihydroxyphosphonates by asymmetric dihydroxylation of vinylphosphonates. An application to the stereocontrolled synthesis of (4S,5S)-4-diethylphosphono-5-hydroxymethyl-2,2-dimethyl-1,3-dioxolane
  作者：Tsutomu Yokomatsu、Yoshinori Yoshida、Kenji Suemune、Takehiro Yamagishi、Shiroshi Shibuya

  DOI：10.1016/0957-4166(95)00014-g

  日期：1995.2

  The asymmetric dihydroxylation (AD) reaction of vinylphosphonates with AD-mix-α and -β reagents was successfully applied to the enantioselective synthesis of threo-α, β-dihydroxyphosphonates. β-Aryl substituents on the vinyl phosphonates were found to be good directors for the reaction with respect to the yield and enantioselectivity. The utility of chiral α, β-dihydroxyphosphonate 2c was illustrated

  与AD混合-α和-β试剂vinylphosphonates的不对称二羟基化（AD）反应成功地应用于的对映选择性合成苏- α，β-dihydroxyphosphonates。发现乙烯基膦酸酯上的β-芳基取代基在产率和对映选择性方面是反应的良好指导。通过立体控制合成（4 S，5 S）-4-二乙基膦酰基-2,2-二甲基-5-羟甲基-1,3-二氧戊环6（一种可能有用的ron ），说明了手性α，β-二羟基膦酸酯2c的用途。 α-杂原子取代的膦酸酯的不对称合成。
• Quinine as chiral discriminator for determination of enantiomeric excess of diethyl 1,2-dihydroxyalkanephosphonates
  作者：Alina Maly、Barbara Lejczak、Pawel Kafarski

  DOI：10.1016/s0957-4166(03)00177-0

  日期：2003.4

  2-dihydroxyethanephosphonates obtained either by chemical or biocatalytic synthesis. Sharpless asymmetric dihydroxylation of diethyl trans-vinylphosphonates enabled differentiation of threo and erythro isomers of 1,2-dihydroxyphosphonates, and provided standards for the determination of the absolute configuration of each of enantiomeric pair of threo isomers.

  奎宁用作31 P NMR变换试剂，用于测定通过化学或生物催化合成获得的对映体过量的1,2-二羟基乙烷膦酸二乙酯。二乙基反式乙烯基膦酸酯的不尖锐的不对称二羟基化使得能够区分1,2-二羟基膦酸酯的苏式和赤型异构体，并为确定每个对映体对苏式异构体的绝对构型提供了标准。
• Enantioselective synthesis of threo-α,β-dihydroxyphosphonates by asymmetric dihydroxylation of 1(E)-alkenylphosphonates with AD-mix reagents
  作者：Tsutomu Yokomatsu、Takehiro Yamagishi、Kenji Suemune、Yoshinori Yoshida、Shiroshi Shibuya

  DOI：10.1016/s0040-4020(97)10341-6

  日期：1998.1

  Asymmetric dihydroxylation (AD) of 1(E)-alkenylphosphonates with an AD-mix -alpha or -beta reagent was examined to give a series of optically active threo-alpha,beta-dihydroxyphosphonates. Good enantioselectivity (>88% eel was observed in the AD reaction of 1(E)-alkenylphosphonates with conjugated aromatic substituents. The steric effects of the ester functionality in the course of the dihydroxylation were also evaluated. Enantioselectivity and yield were significantly improved when the AD reaction was carried out with dimethyl phosphonate instead of diethyl phosphonate. (C) 1997 Elsevier Science Ltd. All rights reserved.