(R)-(+)-(hydroxyphenylmethyl)phosphonic acid diisopropyl ester

• 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: (R)-(+)-(hydroxyphenylmethyl)phosphonic acid diisopropyl ester
• 英文别名: (R)-diisopropyl α-hydroxyphenylmetylphosphonate；(R)-diisopropyl (hydroxy(phenyl)methyl)phosphonate；diisopropyl (R)-[hydroxy(phenyl)methyl]phosphonate；(R)-diisopropyl phenyl(hydroxy)methylphosphonat；diisopropyl (hydroxyl)(phenyl)methylphosphonate；(R)-Diisopropyl hydroxyphenylmethylphosphonate；(R)-di(propan-2-yloxy)phosphoryl-phenylmethanol
• 化学式: C₁₃H₂₁O₄P
• 分子量: 272.281
• InChiKey: QCHMUMZWEDNROG-CYBMUJFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  三异丙基亚磷酸酯 在 盐酸 、 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (S)-(-)-5,5-双(二苯膦基)-4,4-双-1,3-苯并间二氧杂环戊烯 作用下， 以 四氢呋喃 、 水 、 1,2-二氯乙烷 为溶剂， 反应 6.5h， 生成 (R)-(+)-(hydroxyphenylmethyl)phosphonic acid diisopropyl ester
  参考文献：
  名称：

  Rhodium-Catalyzed Enantioselective Cyclizations of γ-Alkynylaldehydes with Acyl Phosphonates: Ligand- and Substituent-Controlled C–P or C–H Bond Cleavage

  摘要：

  It has been established that a cationic rhodium(I)/(R)-H-8-BINAP or (R)-Segphos complex catalyzes two modes of enantioselective cyclizations of gamma-alkynylaldehydes with acyl phosphonates via C-P or C-H bond cleavage. The ligands of the Rh(I) complexes and the substitutents of both gamma-alkynylaldehydes and acyl phosphonates control these two different pathways.

  DOI：

  10.1021/ja201337x

文献信息

• Manganese-proline derived new catalyst system for the enantioselective synthesis of α -hydroxyphosphonates and α -aminophosphonates
  作者：Hyun Lim、Vicklyn Datilus、Rania Teriak、Prianka Chohan、Parminder Kaur

  DOI：10.1016/j.tetlet.2017.02.088

  日期：2017.4

  A novel manganese/proline-derived catalyst system is reported for the stereoselective synthesis of α-hydroxyphosphonates and α-aminophosphonates. The reaction proceeded smoothly under mild reaction conditions with efficient reaction times. The resulting products were obtained with high yields and good enantioselectivities (up to 83% ee).

  报道了一种新颖的锰/脯氨酸衍生的催化剂体系，用于α-羟基膦酸酯和α-氨基膦酸酯的立体选择性合成。反应在温和的反应条件下以有效的反应时间顺利进行。得到的产物具有高收率和良好的对映选择性（高达83％ee）。
• Enzymes in organic chemistry, part 1: Enantioselective hydrolysis of α-(acyloxy)phosphonates by esterolytic enzymes
  作者：Yong-Fu Li、Friedrich Hammerschmidt

  DOI：10.1016/s0957-4166(00)86021-8

  日期：1993.1

  exclusively hydrolyzed to give optically pure alcohols (S)-(−)-3a and (S)-(−)-3b. Lipases AP 6 and F-AP 15 were used to prepare phosphonates (S)-(−)-3b, (S)-(+)-3d and (S)-(−)-3e on a preparative scale with an enantiomeric excess of 81%, 87%, and 89%, respectively. The absolute configurations ofthe α-hydroxyphosphonates were assigned by Horeau's method and 1H-NMR spectroscopy of Mosher's derivatives

  制备α-羟基膦酸酯（±）-3并转化为酯（±）-5。测试了八种脂肪酶以及猪肝酯酶，作为双相系统中α-（酰氧基）膦酸酯的对映选择性水解的催化剂。他们中的两个被证明是有用的。以脂肪酶F-AP 15和α-（乙酰氧基）苯基甲基膦酸酯（±）-5a和（±）-5b为底物可获得最高的对映选择性。（S）-对映异构体专门水解，得到光学纯的醇（S）-（-）- 3a和（S）-（-）- 3b。脂肪酶AP 6和F-AP 15用于制备膦酸酯（S）-（-）- 3b，（S）-（+）- 3d和（S）-（-）- 3e在制备规模上，对映体过量分别为81％，87％和89％。α-羟基膦酸酯的绝对构型通过Horeau法和Mosher衍生物的1 H-NMR光谱确定。
• Asymmetric Hydrogenation of α-Keto Phosphonates with Chiral Palladium Catalysts
  作者：Nataliya S. Goulioukina、Grigorii N. Bondarenko、Alexei V. Bogdanov、Konstantin N. Gavrilov、Irina P. Beletskaya

  DOI：10.1002/ejoc.200800943

  日期：2009.2

  Under atmospheric hydrogen pressure, a catalytic amount of palladium(II) trifluoroacetate and (R)-MeO-BIPHEP in 2,2,2-trifluoroethanol promoted the asymmetric hydrogenation of diisopropyl α-keto phosphonates 1 to afford the corresponding α-hydroxy phosphonates 2 in excellent yields and with a moderate enantioselectivities of up to 55 % ee. Racemic α-aryl-α-hydroxy phosphonates can be prepared by using

  在大气压下，催化量的三氟乙酸钯 (II) 和 (R)-MeO-BIPHEP 在 2,2,2-三氟乙醇中促进二异丙基 α-酮膦酸酯 1 的不对称氢化，得到相应的 α-羟基膦酸酯 2以优异的产率和高达 55% ee 的中等对映选择性。外消旋α-芳基-α-羟基膦酸酯可以用钯碳作为催化剂制备。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Imidazolium ion tethered TsDPENs as efficient ligands for Iridium catalyzed asymmetric transfer hydrogenation of α-keto phosphonates in water
  作者：Mengxia Sun、Joann Campbell、Guowei Kang、Huigang Wang、Bukuo Ni

  DOI：10.1016/j.jorganchem.2016.03.010

  日期：2016.5

  Iridium-catalyzed asymmetric transfer hydrogenation (ATH) of α-ketophosphonates in water. The reaction provided the desired product α-hydroxyphosphonates in moderate to good yields (44–78%) and good to excellent enantioselectivities (up to >99% ee) under mild reaction conditions without adding any surfactants. The enantiomeric excess was determined by 13P NMR by using (−)-cinchonidine as chiral solvating agent

  首次，通过使用咪唑鎓离子束缚的TsDPENs作为铱在水中α-酮膦酸酯的铱催化的不对称转移氢化（ATH）的有效配体，开发了一种有效的方法。该反应在不添加任何表面活性剂的条件下，在温和的反应条件下，以中等至良好的收率（44-78％）和良好至出色的对映选择性（高达> 99％ee）提供了所需的产物α-羟基膦酸酯。通过使用（-）-金可尼定作为手性溶剂化剂，通过13 P NMR测定对映体过量，这是一种比手性HPLC更方便的方法。
• 1,1′-Dibenzyl-bis-(triazolyl)diphenylphosphine dioxide: a new efficient organocatalyst for silicon tetrachloride-mediated enantioselective Abramov-type phosphonylation of aldehydes with trialkyl phosphites
  作者：Nicolas Sevrain、Jean-Noël Volle、Jean-Luc Pirat、Tahar Ayad、David Virieux

  DOI：10.1039/c7ra10919a

  日期：——

  Asymmetric phosphonylation of aldehydes with trialkyl phosphites using a combination of SiCl4 and a novel 1,1′-dibenzyl-bis-(triazolyl)diphenylphosphine dioxide organocatalyst has been developed. This protocol provides the corresponding α-hydroxyphosphonates with a broad range of functional groups and substitution patterns in excellent yields and good selectivities.

  已经开发了使用SiCl 4和新型的1,1'-二苄基-双-（三唑基）二苯基膦二氧化膦有机催化剂组合的醛与亚磷酸三烷基酯的不对称膦酰化反应。该方案以优异的产率和良好的选择性为相应的α-羟基膦酸酯提供了广泛的官能团和取代方式。